Thermoplastic resins and optical components

Abstract

The object of the present invention is to provide a thermoplastic resin having a high refractive index and a low Abbe number and an optical component comprising the same. A thermoplastic resin comprising repeating units represented by the following formula (1), (where Z is a polycyclic aromatic hydrocarbon formed by the condensation of 3 or more benzene rings, L1 and L2 each independently represent a divalent linker, R1 and R2 each independently represent a hydrogen atom, a halogen atom, or a substituent containing 1 to 20 carbon atoms of an aromatic group, j1 and j2 each independently represent an integer of 1 or more, m and n each independently represent 0 or 1, and W is selected from at least one of the group represented by the following formula (2) or (3)) (where X represents a divalent linker).

Description

Technical Field

[0001] This invention relates to thermoplastic resins with high refractive index that can balance heat resistance and formability. Prior Technology

[0002] Camera modules are used in cameras, camcorders, or mobile phones, video phones, or walkie-talkies with cameras. In recent years, there has been a particular demand for miniaturization of the optical systems used in these camera modules. With the miniaturization of optical systems, chromatic aberration has become a significant problem. Therefore, it is known that chromatic aberration correction can be achieved by combining optical lens materials that increase the refractive index and decrease the Abbe number to achieve high dispersion with optical lenses that decrease the refractive index and increase the Abbe number to achieve low dispersion.

[0003] Glass, traditionally used as a material in optical systems, can achieve various required optical properties and has excellent environmental resistance, but it suffers from poor processability. In contrast, resins, which are cheaper and have better processability than glass, have been used in optical components. In particular, resins with a piracene or binaphthalene skeleton are used due to their high refractive index. For example, Patent Documents 1 and 2 describe the use of a high refractive index resin with a refractive index of 1.64 of 9,9-bis(4-(2-hydroxyethoxy)-3-phenyl)piracene. However, the refractive index is insufficient, and a higher refractive index is required. Furthermore, Patent Document 3 describes a thermoplastic resin with 9,9-bis(4-(2-hydroxyethoxy)-3-phenyl)piracene.

[0004] To achieve a high refractive index, Patent Document 4 describes the introduction of aromatic rings into the naphthalene skeleton, and Patent Document 5 describes a thermoplastic resin with aromatic rings introduced into the binaphthalene skeleton. However, with the rapid technological innovation in recent years, there is a demand for even higher refractive indices. [Previous Technical Documents] [Patent Literature]

[0005] Patent Document 1: International Publication No. 2007 / 142149 Patent Document 2: Japanese Patent Application Publication No. 7-198901 Patent Document 3: Japanese Patent Application Publication No. 2015-86265 Patent Document 4: International Publication No. 2019 / 044214 Patent Document 5: International Publication No. 2019 / 044875 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] The problem to be solved by the present invention is to provide a thermoplastic resin having a high refractive index and a low Abbe number and an optical component comprising the same. [Methods used to solve problems]

[0008] Through repeated and active research to achieve these objectives, the inventors discovered that thermoplastic resins containing a structure of three or more benzene rings in cyclization can solve the aforementioned problems, thus completing the present invention. In other words, the present invention is as follows. "State 1" A thermoplastic resin comprising repeating units represented by the following formula (1),

[0009]

[0010] (In the formula, Z refers to polycyclic aromatic hydrocarbons formed by the condensation of three or more benzene rings, L1 and L2 represent divalent linkages, R1 and R2 represent hydrogen atoms, halogen atoms, and substituents with 1 to 20 carbon atoms that may contain aromatic groups, j1 and j2 represent integers of 1 or more, m and n represent 0 or 1, and W is selected from at least one of the groups represented by the following formula (2) or (3).)

[0011]

[0012]

[0013] (In the formula, X represents a divalent linkage base). "State 2" Thermoplastic resin of sample 1, wherein in the aforementioned formula (1), Z is a polycyclic aromatic hydrocarbon of the phenanthrene type. Appearance 3 Thermoplastic resins such as state 1 or 2, wherein in the aforementioned formula (1), Z is a polycyclic aromatic hydrocarbon formed by the condensation of 3 or 4 benzene rings. Appearance 4 Thermoplastic resin of any one of the states 1 to 3, wherein in the aforementioned formula (1), Z is phenanthrene. Appearance 5 For any of the thermoplastic resins in samples 1 to 4, the repeating unit represented by the aforementioned formula (1) is represented by the following formula (4).

[0014]

[0015] (In the formula, L1 and L2 represent divalent linkages independently, R3 and R4 represent hydrogen atoms, halogen atoms, and substituents of 1 to 20 carbon atoms that may contain aromatic groups independently, j3 and j4 represent integers of 1 or more independently, m and n represent 0 or 1 independently, and W is selected from at least one of the groups represented by the aforementioned formula (2) or (3). Appearance 6 Thermoplastic resin of any one of states 1 to 4, wherein in the aforementioned formula (1), R1 and R2 independently represent hydrogen atom, methyl, phenyl or naphthyl. "State 7" Thermoplastic resin of sample 5, wherein in the aforementioned formula (4), R3 and R4 independently represent hydrogen atom, methyl, phenyl or naphthyl respectively. "State 8" The thermoplastic resin of any one of states 1 to 7, wherein X in formula (3) is selected as a repeating unit from the group consisting of at least one of the groups represented by phenyl, naphthyl, groups represented by formula (5) below, and groups represented by formula (6) below.

[0016]

[0017] (In the formula, R5 and R6 are hydrogen atoms, and may contain 1 to 20 carbon substituents or halogen atoms of aromatic groups, respectively.)

[0018] .

[0019] "Style 9" The thermoplastic resin of any one of the states 1 to 8, wherein at least one of the units selected from the group of units represented by the following formulas (7) to (10) is used as a repeating unit,

[0020]

[0021] (In the formula, R7 and R8 are hydrogen atoms, and may contain 1 to 20 carbon substituents or halogen atoms of aromatic groups, respectively.)

[0022]

[0023] (In the formula, R9 and R10 are hydrogen atoms, and may contain 1 to 20 carbon substituents or halogen atoms of aromatic groups, respectively.)

[0024]

[0025] (In the formula, R11 and R12 are hydrogen atoms, and may contain 1 to 20 carbon substituents or halogen atoms of aromatic groups, respectively.)

[0026]

[0027] (In the formula, R13 and R14 are hydrogen atoms, substituents with 1 to 20 carbon atoms that may contain aromatic groups, or halogen atoms, U-series single bonds or divalent linkages, respectively). "Style 10" Thermoplastic resins of any one of states 1 to 9, wherein the refractive index is 1.65 to 1.80. "Style 11" Thermoplastic resin of any one of samples 1 to 10, wherein the specific viscosity is 0.12 to 0.40. "Style 12" The thermoplastic resin of any one of the states 1 to 11, wherein the glass transition temperature is 130 to 170°C. Appearance 13 An optical component made of any one of the thermoplastic resins described in samples 1 to 12. Appearance 14 The optical component of sample 13 is an optical lens. [Invention Effects]

[0028] The thermoplastic resin of this invention has a high refractive index and a low Abbe number, so it can be used in optical components such as optical lenses, prisms, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coatings. It is especially useful in optical lenses used in mobile phones, smartphones, tablet terminals, personal computers, digital cameras, camcorders, vehicle cameras, or surveillance cameras. Therefore, it has excellent industrial effects. Simple Explanation of the Diagram

[0029] [Figure 1] is the transmission spectrum of 0.1% by mass dichloromethane solution of thermoplastic resin in Example 1 and Comparative Example 2. Implementation

[0030] The present invention will be described in further detail. <Thermoplastic Resins> Thermoplastic resin comprising repeating units represented by the following formula (1).

[0031]

[0032] (In the formula, Z refers to polycyclic aromatic hydrocarbons formed by the condensation of three or more benzene rings, L1 and L2 represent divalent linkages, R1 and R2 represent hydrogen atoms, halogen atoms, and substituents with 1 to 20 carbon atoms that may contain aromatic groups, j1 and j2 represent integers of 1 or more, m and n represent 0 or 1, and W is selected from at least one of the groups represented by the following formula (2) or (3).)

[0033]

[0034]

[0035] (In the formula, X represents a divalent linkage group). In the aforementioned formula (1), Z is a polycyclic aromatic hydrocarbon formed by the condensation of three or more benzene rings, preferably a polycyclic aromatic hydrocarbon formed by the condensation of three or four benzene rings, and more preferably a polycyclic aromatic hydrocarbon formed by the condensation of three benzene rings.

[0036] Furthermore, in the aforementioned formula (1), the polycyclic aromatic hydrocarbon of Z is preferably a structure in which the benzene ring is condensed into a acene or phenanthrene type, and more preferably a structure in which the ring is condensed into a phenanthrene type.

[0037] In the aforementioned formula (1), Z is preferably phenanthrene, anthracene, phenanthrene, chrysene, tetraphenyl, or pyrene, more preferably phenanthrene, anthracene, chrysene, or tetraphenyl. Based on the viewpoint of stability due to differences in molecular orbitals at the leading edge when the number of rings increases, it is even more preferably phenanthrene or chrysene. Based on the viewpoint of absorption wavelength, it is particularly preferably phenanthrene.

[0038] In the aforementioned formula (1), R1 and R2 independently represent hydrogen atoms, halogen atoms, and substituents with 1 to 20 carbon atoms that may contain aromatic groups, preferably hydrogen atoms, methyl, phenyl, naphthyl, thiophene, benzothiophene, more preferably hydrogen atoms, methyl, phenyl, naphthyl, even more preferably hydrogen atoms and methyl, and most preferably hydrogen atoms.

[0039] Furthermore, fluorine, chlorine, and bromine atoms are preferred as halogen atoms.

[0040] It can also be a substituent with 1 to 12 carbon atoms that can contain an aromatic group, preferably phenyl, naphthyl, thiophene, or benzothiophene.

[0041] Furthermore, as a specific example of naphthyl, 1-naphthyl or 2-naphthyl are preferred.

[0042] Specific examples of thiophene groups are preferably 2-thiophene or 3-thiophene.

[0043] Specific examples of benzo[b]thiophene group are preferably 2-benzo[b]thiophene group or 3-benzo[b]thiophene group.

[0044] In the aforementioned formula (1), L1 and L2 independently represent divalent linkers, preferably alkyl groups with 1 to 12 carbon atoms, more preferably alkyl groups with 1 to 4 carbon atoms, and even more preferably ethyl groups. By adjusting the length of the linkers L1 and L2, the glass transition temperature (Tg) of the resin can be adjusted.

[0045] In the aforementioned formula (1), W is selected from at least one of the group represented by the aforementioned formula (2) or (3). When W is the aforementioned formula (2), the aforementioned formula (1) becomes a carbonate unit, and when W is the aforementioned formula (3), the aforementioned formula (1) becomes an ester unit.

[0046] Formula (1) can be obtained from carbonate precursors such as dihydroxy compounds and carbonates, or dihydroxy compounds and dicarboxylic acids or their ester-forming derivatives.

[0047] In the aforementioned formula (1), m and n independently represent 0 or 1, with 1 being preferred.

[0048] In the aforementioned formula (1), j1 and j2 are integers greater than or equal to 1, preferably integers from 1 to 4, and even more preferably 1.

[0049] Furthermore, the repeating unit represented by the aforementioned formula (1) is preferably the repeating unit represented by the following formula (4).

[0050]

[0051] (In the formula, R3 and R4 represent hydrogen atoms, halogen atoms, and substituents with 1 to 20 carbon atoms that may contain aromatic groups, respectively; j3 and j4 represent integers greater than 0, respectively; L1, L2, m, n and W are the same as in the aforementioned formula (1).) In the aforementioned formula (4), R3 and R4 independently represent hydrogen atoms, halogen atoms, and substituents with 1 to 20 carbon atoms that may contain aromatic groups, preferably hydrogen atoms, methyl, phenyl, naphthyl, thiophene, benzothiophene, more preferably hydrogen atoms, methyl, phenyl, naphthyl, even more preferably hydrogen atoms and methyl, and most preferably hydrogen atoms.

[0052] In the aforementioned formula (4), j3 and j4 are integers greater than or equal to 1, preferably integers from 1 to 4, and even more preferably 1.

[0053] In the aforementioned formula (3), X represents a divalent linkage group, preferably a substituent containing an aromatic group with 1 to 30 carbon atoms, and more preferably a phenyl, naphthyl, or a group represented by the following formula (5) or formula (6).

[0054]

[0055] (In the formula, R5 and R6 are hydrogen atoms, substituents with 1 to 20 carbon atoms of aromatic groups, or halogen atoms, respectively).

[0056]

[0057] In the aforementioned formula (5), R5 and R6 independently represent a hydrogen atom, a halogen atom, and a substituent containing 1 to 20 carbon atoms of an aromatic group, respectively. Preferably, they are hydrogen atoms, methyl, phenyl, naphthyl, thiophene, or benzothiophene, more preferably hydrogen atoms, methyl, phenyl, or naphthyl, even more preferably hydrogen atoms and methyl, and most preferably hydrogen atoms.

[0058] The reasons for achieving the effects of this invention, namely, a high refractive index and a low Abbe number, are as follows.

[0059] In patent documents 4 and 5, the refractive index is increased by introducing aromatic groups with single bonds. From the relationship between molecular structure and refractive index known as the Lorentz-Lorenz formula, it is known that the refractive index of a substance can be increased by increasing the polarizability of the molecule, while the Abbe number is also reduced.

[0060] This invention enables the production of resins with high refractive index and low Abbe number that were previously unattainable using conventional techniques. Because the polarizability is increased more significantly by incorporating aromatic groups through a three- or more ring-condensation structure than by introducing aromatic groups through single bonds, it is believed that a high refractive index can be achieved.

[0061] Furthermore, the introduction of aromatic rings into the phenanthrene structure is believed to resolve the contradiction between increasing refractive index and extending absorption wavelength, a problem that has plagued previous techniques. For example, in the case of a phenyl group introduced at the 6,6-position in a biphenylene structure and in the case of a biphenylene group, although the number of aromatic rings only increases by two, the biphenylene group exhibits a higher refractive index and can also suppress the extension of absorption wavelength. Therefore, the phenanthrene structure is considered useful for constructing materials for optical applications.

[0062] The repeating unit represented by the aforementioned formula (1) may contain 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, or may contain less than 100 mol%, less than 90 mol%, less than 80 mol%, less than 70 mol%, less than 60 mol% or less, or less than 50 mol%. The resin of the present invention, represented by the repeating unit of the aforementioned formula (1), preferably contains 10 mol% or more and less than 100 mol%, more preferably 20 mol% or more and less than 100 mol%, more preferably 20 mol% or more and less than 80 mol%, and most preferably 20 mol% or more and less than 70 mol%. If the repeating unit represented by the aforementioned formula (1) falls within the aforementioned range, the balance of refractive index, heat resistance, and formability is excellent, thus it is preferable.

[0063] The thermoplastic resin of the present invention may contain at least one repeating unit selected from the group of units represented by the aforementioned formulas (7) to (10).

[0064]

[0065] (In the formula, R7 and R8 are the same as R5 and R6 in the aforementioned formula (5).)

[0066]

[0067] (In the formula, R9 and R10 are the same as R5 and R6 in the aforementioned formula (5).)

[0068]

[0069] (In the formula, R11 and R12 are the same as R5 and R6 in the aforementioned formula (5).)

[0070]

[0071] (In the formula, R13 and R14 are the same as R5 and R6 in the aforementioned formula (5), and U represents a single bond or a divalent linkage). The molar ratio of the repeating unit represented by the aforementioned formula (1) to the repeating unit of the group formed by the units represented by the aforementioned 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. If the molar ratio of the repeating unit represented by the aforementioned formula (1) to at least one repeating unit selected from the group formed by the units represented by the aforementioned formulas (7) to (10) is within the aforementioned range, then in addition to the high refractive index, the balance of formability is also excellent, which is therefore better. Properties of Thermoplastic Resins The specific viscosity of the thermoplastic resin of the present invention is preferably 0.12~0.40, more preferably 0.14~0.35, and even more preferably 0.16~0.30. If the specific viscosity is within the above range, the balance between formability and mechanical strength is excellent, and therefore preferred.

[0072] The specific viscosity was determined by measuring the specific viscosity (ηSP) of a solution containing 0.7g of thermoplastic resin dissolved in 100ml of dichloromethane at 20°C using an Ubbelohde viscometer, and calculated using the following formula.

[0073] Specific viscosity (ηSP) = (t - t0) / t0 [t0 represents the number of seconds it takes for dichloromethane to fall, and t represents the number of seconds it takes for the sample solution to fall.] The refractive index of the thermoplastic resin of this invention, measured at 20°C and 587.56 nm, is 1.650 or higher, and may also be 1.660 or higher, 1.670 or higher, 1.680 or higher, 1.690 or higher, or 1.700 or higher, and may be 1.800 or lower, 1.790 or lower, 1.780 or lower, 1.770 or lower, 1.760 or lower, or 1.750 or lower. Preferably, it is 1.650 to 1.800, more preferably 1.670 to 1.800, and even more preferably 1.680 to 1.800. When the refractive index is above the lower limit, the spherical aberration of the optical lens can be reduced, thereby shortening the focal distance of the optical lens.

[0074] The thermoplastic resin of this invention has a high refractive index, but preferably a low Abbe number.

[0075] The Abbe number of the thermoplastic resin of the present invention can be 5 or more, 7 or more, 9 or more, 10 or more, 12 or more, or 14 or more, and can 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.

[0076] Here, the Abbe number system is calculated using the following formula for the refractive index at a temperature of 20℃ and wavelengths of 486.13nm, 587.56nm, and 656.27nm: νd=(nd-1) / (nF-nC) nd: Refractive index at wavelength 587.56nm nF: Refractive index at wavelength 486.13nm nC: Refractive index at a wavelength of 656.27 nm.

[0077] The glass transition temperature (Tg) of the thermoplastic resin system of the present invention can be above 130°C, above 135°C, above 140°C, above 145°C, or above 150°C, or below 180°C, below 175°C, below 170°C, below 165°C, or below 160°C. Preferably, it is 130~180°C, more preferably 140~175°C, and even more preferably 140~170°C. If the glass transition temperature is within the above range, the balance between heat resistance and formability is excellent and superior.

[0078] The absolute value (|Δn|) of the alignment birefringence of the thermoplastic resin of the present invention is preferably 10.0 × 10⁻³ or less, may be 5.0 × 10⁻³ or less, but is more preferably 3.0 × 10⁻³ or less. If |Δn| is within the above range, the optical distortion of the optical lens is reduced, which is therefore preferred.

[0079] Δn is calculated by stretching a 100 μm thick film obtained from the thermoplastic resin of the present invention by 2 times at a temperature of Tg+10°C, measuring the phase difference at a wavelength of 589 nm, and then using the following formula.

[0080] |Δn|=|Re / d| Δn: Alignment birefringence Re: Phase difference (nm) d: thickness (nm) The water absorption rate of the thermoplastic resin of the present invention after immersion in water at 23°C for 24 hours is preferably 0.25% by mass or less, and more preferably 0.20% by weight or less. If the water absorption rate is within the above range, the change in optical properties caused by water absorption is smaller, which is therefore preferable.

[0081] The thermoplastic resin of the present invention preferably has a spectral transmittance of 40% or more at 360 nm, more preferably 50% or more, even more preferably 60% or more, and most preferably 70% or more. If it is within the above range, visible light can pass through, which is preferable. <Raw Materials of Thermoplastic Resins> (Diol component of formula (1)) The diol component of formula (1) as a raw material is mainly the diol component represented by formula (a), which can be used alone or in combination of two or more.

[0082]

[0083] In the aforementioned equation (a), Z, R1, R2, L1, L2, j1, j2, m, and n are the same as those in the aforementioned equation (1).

[0084] The following are representative examples of diol components represented by the aforementioned formula (a), but the raw materials used in the aforementioned formula (1) are not limited to these.

[0085] Among the diol compounds represented by formula (1), examples include bianthraphenols, biphenanthrophenols, biphenenols, biphenyltetraphenols, biphenylphenols, and bipyrene phenols. Specifically, preferred examples include 2,2'-dihydroxy-1,1'-bianthracite, 10,10'-dihydroxy-9,9'-bianthracite, 2,2'-dihydroxy-1,1'-biphenanthrene, 3,3'-dihydroxy-4,4'-biphenanthrene, 10,10'-dihydroxy-9,9'-biphenanthrene, 2,2'-dihydroxy-1,1'-biphenanthrene, 3,3'-dihydroxy-2,2'-biphenyl, 12,12'-dihydroxy-5,5'-biphenyl, 3,3'-dihydroxy-4,4'-biphenyl, 5,5'-dihydroxy-6,6'-biphenyl, 2,2'-dihydroxy-1,1-bipyrene, and 7,7'-dihydroxy-2,2'-biphenyl, all represented by the following formula (a-1). Pyrene, 2,2'-bis(2-hydroxyethoxy)-1,1'-bianthracene, 10,10'-bis(2-hydroxyethoxy)-9,9'-bianthracene, 2,2'-bis(2-hydroxyethoxy)-1,1'-biphenanthrene, 3,3'-bis(2-hydroxyethoxy)-4,4'-biphenanthrene, 10,10'-bis(2-hydroxyethoxy)-9,9'-biphenanthrene, 2,2'-bis(2-hydroxyethoxy)-1,1'-biphenanthrene, 3,3'-bis(2-hydroxyethoxy)-2,2'-biphenanthrene, 12,12'-bis(2-hydroxyethoxy)-5,5'-biphenanthrene, 3,3'-bis(2-hydroxyethoxy)-4 ,4'-biphenyl, 5,5'-bis(2-hydroxyethoxy)-6,6'-biphenyl, 2,2'-bis(2-hydroxyethoxy)-1,1-bipyrene, 7,7'-bis(2-hydroxyethoxy)-2,2'-bipyrene, more preferably 2,2'-dihydroxy-1,1'-biphenanthrene, 3,3'-dihydroxy-4,4'-biphenanthrene, 10,10'-dihydroxy-9,9'-biphenanthrene, 3,3'-dihydroxy-4,4'-biphenyl, 5,5'-dihydroxy-6,6'-biphenyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-biphenanthrene, 3,3'-bis(2-hydroxyethoxy)-4,4'-biphenanthrene, 10,10'-bis(2-hydroxyethoxy)- 9,9'-Bis(2-hydroxyethoxy)-4,4'-Bis(2-hydroxyethoxy)-6,6 ...

[0086]

[0087]

[0088] (The carbonate component of the aforementioned formula (1)) Examples of carbonate components used in the thermoplastic resin of the present invention, expressed in units of the aforementioned formula (1), include phosgene and carbonate. Examples of carbonates include esters of aryl, aralkyl, or alkyl groups having 6 to 10 carbon atoms that can be substituted. Specific examples include diaryl carbonates such as diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, bis(m-tolyl) carbonate, and dinaphthalene carbonate; dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate; alkyl carbonates such as ethyl phenyl carbonate and cyclohexyl phenyl carbonate; or diene carbonates such as divinyl carbonate, diisopropylene carbonate, and dipropylene carbonate, with diaryl carbonate being preferred, and diphenyl carbonate being more preferred. (The dicarboxylic acid component of formula (1) above) The dicarboxylic acid component used in the thermoplastic resin of the present invention, expressed in units of the aforementioned formula (1), is preferably a dicarboxylic acid or its ester-forming derivative expressed in formula (b).

[0089]

[0090] In the aforementioned equation (b), X represents a 2-valent linkage base, which can be said to be the same as that described in the aforementioned equation (3).

[0091] The following are representative examples of dicarboxylic acids or their ester-forming derivatives represented by the aforementioned formula (b), but the raw materials used as the aforementioned formula (b) of this invention are not limited thereto.

[0092] Examples of dicarboxylic acid components used in the thermoplastic resin of this invention include 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) benzo[a], which are raw materials of the aforementioned formula (6). Other examples include malonic acid and amber. Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid; monocyclic aromatic dicarboxylic acids 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)enyl, and 9,9-bis(1-carboxyethyl)enyl. Polycyclic aromatic dicarboxylic acid components such as 9,9-bis(1-carboxypropyl)fucose, 9,9-bis(2-carboxypropyl)fucose, 9,9-bis(2-carboxy-1-methylethyl)fucose, 9,9-bis(2-carboxy-1-methylpropyl)fucose, 9,9-bis(2-carboxybutyl)fucose, 9,9-bis(2-carboxy-1-methylbutyl)fucose, 9,9-bis(5-carboxypentyl)fucose, and 9,9-bis(carboxycyclohexyl)fucose, 2,2'-bi The derivatives include biphenyl dicarboxylic acid (BDI) such as phenyl dicarboxylic acid, alicyclic dicarboxylic acid (ACA) such as 1,4-cyclohexanedicarboxylic acid, and 2,6-dodecanedicarboxylic acid, preferably isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and 9,9-bis(2-carboxyethyl)carboxylic acid, more preferably 2,6-naphthalenedicarboxylic acid, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, and 9,9-bis(2-carboxyethyl)carboxylic acid. These derivatives can be used alone or in combination of two or more. Furthermore, esters such as chlorophenyl, methyl ester, ethyl ester, and phenyl ester can also be used as ester-forming derivatives. (Components of the aforementioned formulas (7) to (10)) The thermoplastic resin of the present invention may further have dihydroxy compounds in which the raw materials of the aforementioned formulas (7) to (10) are repeated units, as shown below. These can be used alone or in combination of two or more.

[0093] Examples of dihydroxy compounds that can be used as raw materials in 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.

[0094] Examples of dihydroxy compounds that serve as raw materials in formula (8) of this invention include 9,9-bis(4-(2-hydroxyethoxy)benzyl), 9,9-bis(4-(2-hydroxyethoxy)phenyl)benzyl, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)benzyl, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)benzyl, and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)benzyl, with 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)benzyl being particularly preferred. These compounds can be used alone or in combination of two or more.

[0095] Examples of dihydroxy compounds that can be used as raw materials in formula (9) of the present invention include 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl) fumaride and 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-2,7-diphenylfumaride.

[0096] Examples of dihydroxy compounds that serve as raw materials for the aforementioned formula (10) of this 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, and 1,1-bis( 4-Hydroxyphenyl)decane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, biphenol, 9,9-bis(4-hydroxyphenyl)furan, 9,9-bis(4-hydroxy-3-methylphenyl)furan, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)furan, 9,9-bis(4-hydroxy-3-phenylphenyl)furan, bis(4-hydroxyphenyl) tannin, 10,10-bis(4-hydroxyphenyl)anthrone, etc., with 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)sulfide being particularly preferred. These can be used alone or in combination of two or more. (Copolymer components other than those in formulas (1) to (10) above) The thermoplastic resin of this invention can be copolymerized with other dihydroxy compounds to a degree that does not impair the characteristics of this invention. Preferably, the other dihydroxy compounds do not exceed 30 mol% of the total repeating units.

[0097] Examples of other dihydroxy compounds used in the thermoplastic resins of this invention include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo[5.2.1.02,6]decanediethanol, cyclohexane-1,4-diethanol, decane-2,6-diethanol, norbornenediethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-diethanol, spirodiol, isosorbide, disohydrate isomannitol, disohydrate idulol, hydroquinone, resorcinol, bis(4-(2-hydroxyethoxy)phenyl) benzoyl, 1,1'-bi-2-naphthol, dihydroxynaphthalene, bis(2-hydroxyethoxy)naphthalene, etc., which may be used alone or in combination of two or more.

[0098] The thermoplastic resin of the present invention is manufactured by methods such as reacting a dihydroxy compound component with a carbonate precursor such as phosgene or diester, or reacting a diol component with a dicarboxylic acid or its ester-forming derivative. Specific examples are shown below. <Manufacturing Method> (Manufacturing method of polycarbonate resin) When the thermoplastic resin of this invention is a polycarbonate resin, it can be obtained by reacting the dihydroxy compound component with a carbonate precursor using known reaction methods, such as interfacial polymerization or melt polymerization. When manufacturing the polycarbonate resin, catalysts, end-stopping agents, antioxidants, etc., may also be used as needed. (Manufacturing method of polyester resin) When the thermoplastic resin of the present invention is a polyester resin, it can be produced by using known reaction methods, such as esterification or transesterification of the dihydroxy compound with dicarboxylic acid or its ester-forming derivatives, and the resulting reaction product can be subjected to polycondensation reaction to produce a high molecular weight polymer of the desired molecular weight. (Manufacturing method of polyester carbonate resin) When the thermoplastic resin of the present invention is a polyester carbonate resin, it can be manufactured by reacting a dihydroxy compound component and a dicarboxylic acid or its ester-forming derivative with a carbonate precursor such as phosgene or carbonate. The polymerization method can be the same as that used for the aforementioned polycarbonate resin or polyester resin. <Optical Components> The optical components of the present invention comprise the aforementioned thermoplastic resin. There are no particular limitations on the optical components used for optical applications where the thermoplastic resin is useful; examples include optical lenses, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard-coated films, etc.

[0099] Furthermore, the optical component of the present invention may be composed of a resin composition containing the above-mentioned thermoplastic resin, wherein additives such as heat stabilizers, plasticizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, and antioxidants may be added as needed.

[0100] Examples of 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-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Tributyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoylamine), diethyl 3,5-di-tert-butyl-4-hydroxy-phenyl phosphate, 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)propoxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, etc. The amount of antioxidant, relative to 100 parts by weight of the thermoplastic resin composition, is preferably 0.50 parts by weight or less, more preferably 0.05 to 0.40 parts by weight, even more preferably 0.05 to 0.20 parts by weight or 0.10 to 0.40 parts by weight, and particularly preferably 0.20 to 0.40 parts by weight. <Optical Lenses> As an optical component of the present invention, an optical lens is particularly exemplified. Examples of such optical lenses include those used in mobile phones, smartphones, tablet terminals, personal computers, digital cameras, camcorders, vehicle cameras, surveillance cameras, etc.

[0101] The optical lens of the present invention can be formed and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is preferred.

[0102] There are no particular restrictions on the molding conditions for injection molding, but the cylinder temperature of the molding machine is preferably 180~320℃, more preferably 220~300℃, and even more preferably 240~280℃. The mold temperature is preferably 70~130℃, more preferably 80~125℃, and even more preferably 90~120℃. The injection pressure is preferably 5~170MPa, more preferably 50~160MPa, and even more preferably 100~150MPa.

[0103] The present invention will be further illustrated by the following embodiments, but the present invention is not limited thereto. [Example]

[0104] Manufacturing Examples [Example 1] 9.50 parts by weight (20 moles) of 10,10'-bis(2-hydroxyethoxy)-9,9'-biphenanthrene (hereinafter sometimes abbreviated as BHEBPhe), 35.08 parts by weight (80 moles) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]enazine (hereinafter sometimes abbreviated as BPEF), 21.64 parts by weight (101 moles) of diphenyl carbonate (hereinafter sometimes abbreviated as DPC) and 8.40 × 10⁻⁵ parts by weight (1.00 × 10⁻³ moles) of sodium bicarbonate at a concentration of 60 mmol / L as a catalyst were added, and the mixture was heated to 180°C under nitrogen atmosphere to melt. Then, the pressure was adjusted to 20 kPa over 5 minutes. The temperature was increased to 250°C at a rate of 60°C / hr until the phenol flow rate reached 70%, and then the pressure was reduced to 60 kPa / hr to carry out the polymerization reaction until the desired electrical charge was reached. After the reaction was completed, the resin was removed from the flask. The obtained polycarbonate resin was analyzed by 1H NMR, confirming the introduction of 20 mol% of 10,10'-bis(2-hydroxyethoxy)-9,9'-biphenanthrene relative to all monomers. Using this polycarbonate resin, the copolymerization ratio, refractive index, Abbe number, Tg, and light transmittance at 360 nm and 500 nm were evaluated, and the results are shown in Table 1. [Example 2] Except for changing BHEBPhe and BPEF to the ratios shown in Table 1, the polycarbonate resin was manufactured in the same manner as in Example 1. Using this polycarbonate resin, the copolymerization ratio, refractive index, Abbe number, Tg, and light transmittance at 360 nm and 500 nm were evaluated, and the results are shown in Table 1. [Example 3] Except for changing BHEBPhe to the ratios listed in Table 1, the polycarbonate resin was manufactured in the same manner as in Example 1. Using this polycarbonate resin, the copolymerization ratio, refractive index, Abbe number, Tg, and light transmittance at 360 nm and 500 nm were evaluated, and the results are shown in Table 1. [Example 4] Except that BHEBPhe, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (hereinafter sometimes referred to as BHEB), and 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl (hereinafter sometimes referred to as BCMB) were used in the ratios described in Table 1, the DPC was changed to 4.50 parts by weight (21 moles), and 3.4 × 10⁻³ parts by weight (1.00 × 10⁻² moles) of tetrabutyl titanium oxide were used as catalysts, the polyester carbonate resin was manufactured in the same manner as in Example 1. Using this polyester carbonate resin, the copolymerization ratio, refractive index, Abbe number, Tg, and light transmittance at 360 nm and 500 nm were evaluated, and the results are shown in Table 1. [Comparative Examples 1-3] By changing the composition of Example 1 to that described in Table 1, particles of the polycarbonate resin of Comparative Examples 1 to 3 were obtained. Using this polycarbonate resin, the copolymerization ratio, refractive index, Abbe number, Tg, and light transmittance at 360 nm and 500 nm were evaluated, and the results are shown in Table 1.

[0105] The obtained thermoplastic resin was evaluated using the following method. <Copolymer ratio> The composition ratio of each polymer was calculated by measuring the 1H NMR of the obtained resin using a JNM-ECZ400S instrument manufactured by Nippon Electronics Co., Ltd. CDCl3 was used as the solvent. <Optical Properties> (Refractive index) After preparing and grinding 3 mm thick test pieces for each polymer, the refractive index nd (587.56 nm) at 20 °C was measured using a Shimadzu KPR-2000 carbon precision refractometer. (Abbe number) The Abbe number is measured at wavelengths from the refractive indices of 486.13 nm, 587.56 nm, and 656.27 nm using the following formula.

[0106] νd=(nd-1) / (nF-nC) nd: Refractive index at wavelength 587.56nm nF: Refractive index at wavelength 486.13nm nC: Refractive index at wavelength 656.27nm (Absolute value of alignment birefringence) Thermoplastic resin was dissolved in dichloromethane and cast onto a glass dish. After thorough drying, a 100 μm thick casting film was prepared. The film was stretched twice at Tg+10℃, and the phase difference (Re) at 589 nm was measured using a Japanese spectrophotometer M-220. The absolute value of the alignment birefringence (|Δn|) was calculated using the following formula.

[0107] |Δn|=|Re / d| Δn: Alignment birefringence Re: Phase difference (nm) d: thickness (nm) (Light transmittance) Dissolve 6.7 mg of the obtained resin in 5 mL of dichloromethane (specific gravity: 1.33 g / mL) to prepare a 0.1% by mass solution. The transmittance of this solution from 250 nm to 780 nm was measured using a Hitachi U-3310 spectrophotometer. <Glass transition temperature (Tg)> The obtained resin was tested using a Discovery DSC25Auto model manufactured by TI INSTRUMENTS, Japan, at a heating rate of 20°C / min. Samples were tested in the range of 5–10 mg. "result" The evaluation results of examples related to thermoplastic resins are shown in Table 1. In addition, the transmission spectra of 0.1% by mass dichloromethane solutions of the thermoplastic resins of Example 1 and Comparative Example 2 are shown in Figure 1.

[0108]

[0109] Examples 1-4 using BHEBPhe exhibit high refractive index and low Abbe number, demonstrating excellent results as optical lenses.

[0110] Furthermore, since both Comparative Example 1 and Comparative Example 2 are constructed by adding an aromatic ring to the naphthalene of Comparative Example 1, it can be seen that the absorption wavelength of Comparative Example 1 was suppressed by increasing the wavelength.

[0111] By using polycyclic aromatic hydrocarbons with more than three benzene rings condensed into repeating units as in formula (1), the polarizability can be improved, and both high refractive index and high Abbe number can be effectively achieved. [Industrial Applicability]

[0112] The thermoplastic resin of this invention is used in optical materials and can be used in optical components such as optical lenses, prisms, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coatings, and is especially useful for optical lenses.

Claims

1. A thermoplastic resin comprising repeating units represented by the following formula (1), (where Z is a polycyclic aromatic hydrocarbon of the phenanthrene type formed by the condensation of three or more benzene rings, L1 and L2 each independently represent a divalent linker of an alkyl group having 1 to 4 carbon atoms, R1 and R2 each independently represent a hydrogen atom, a halogen atom, or a substituent having 1 to 20 carbon atoms that may contain an aromatic group, j1 and j2 each independently represent an integer of 1 or more, m and n each represent 1, and W is selected from at least one of the group represented by the following formula (2) or (3), (where X represents a divalent linker).

2. The thermoplastic resin of claim 1, wherein in the aforementioned formula (1), Z is a polycyclic aromatic hydrocarbon formed by the condensation of 3 or 4 benzene rings.

3. The thermoplastic resin of claim 2, wherein Z in the aforementioned formula (1) is phenanthrene.

4. The thermoplastic resin of claim 1 or 2, wherein the repeating unit represented by the aforementioned formula (1) is represented by the following formula (4), (where L1 and L2 independently represent divalent linkages of alkyl groups having 1 to 4 carbon atoms, R3 and R4 independently represent hydrogen atoms, halogen atoms, and substituents having 1 to 20 carbon atoms that may contain aromatic groups, j3 and j4 independently represent integers of 1 or more, m and n each represent 1, and W is selected from at least one of the group represented by the aforementioned formula (2) or (3).

5. The thermoplastic resin of claim 1 or 2, wherein in the aforementioned formula (1), R1 and R2 independently represent a hydrogen atom, methyl, phenyl or naphthyl group, respectively.

6. The thermoplastic resin of claim 4, wherein in the aforementioned formula (4), R3 and R4 independently represent a hydrogen atom, methyl, phenyl or naphthyl group, respectively.

7. The thermoplastic resin of claim 1 or 2, wherein X in the aforementioned formula (3) is selected as a repeating unit from at least one of the groups of phenyl, naphthyl, groups represented by the following formula (5) and groups represented by the following formula (6), (where R5 and R6 are independently hydrogen atoms, substituents containing 1 to 20 carbon atoms of aromatic groups, or halogen atoms, respectively).

8. The thermoplastic resin of claim 1 or 2, comprising at least one of the groups of units represented by the following formulas (7) to (10) as repeating units, (where R7 and R8 are each independently hydrogen atoms, substituents of 1 to 20 carbon atoms containing aromatic groups, or halogen atoms), (where R9 and R10 are each independently hydrogen atoms, substituents of 1 to 20 carbon atoms containing aromatic groups, or halogen atoms), (where R11 and R12 are each independently hydrogen atoms, substituents of 1 to 20 carbon atoms containing aromatic groups, or halogen atoms), (where R13 and R14 are each independently hydrogen atoms, substituents of 1 to 20 carbon atoms containing aromatic groups, or halogen atoms, U-type single bonds or divalent linkages).

9. The thermoplastic resin of claim 1 or 2, wherein the refractive index is 1.65 to 1.

80.

10. The thermoplastic resin of claim 1 or 2, wherein the specific viscosity is 0.12 to 0.

40.

11. The thermoplastic resin of claim 1 or 2, wherein the glass transition temperature is 130~170°C.

12. An optical component made of a thermoplastic resin as claimed in any one of claims 1 to 11.

13. The optical component of claim 12 is an optical lens.

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