Diol compound, optical resin, polycarbonate resin, and optical molded body

Abstract

To provide: a diol compound that can improve the refractive index of an optical resin; and an optical resin, a polycarbonate resin and an optical molding improved in the refractive index.SOLUTION: The diol compound is represented by the general formula (1) in the figure. In the general formula (1), Ar1 to Ar5 each independently represent a hydrocarbon or heterohydrocarbon group; each of a to e independently represents 0 or an integer of 1 to 2; each of o and p independently represents an integer of 1 to 6.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a diol compound, an optical resin, a polycarbonate resin, and an optical molded article. [Background technology]

[0002] Optical glass or optical resin is used as a material for optical lenses used in the optical systems of various cameras, such as cameras with integrated film and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of optical glass with various refractive indices and Abbe numbers. However, there are problems such as high material costs, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage of being mass-produced by injection molding. For example, polycarbonate resins are used in camera lenses. However, in recent years, the trend toward lighter, thinner, and smaller products has led to a demand for the development of resins with higher refractive indices. Generally, when the refractive index of an optical material is high, lens elements with the same refractive index can be realized with surfaces having smaller curvatures, thereby reducing the amount of aberration generated by these surfaces. As a result, it becomes possible to reduce the number of lenses, reduce the lens's decentering sensitivity, and reduce the lens's thickness to reduce its weight.

[0004] Techniques relating to optical resins include those described in Patent Documents 1, 2 and 3, for example.

[0005] Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-241962) describes an optical lens made of a polycarbonate resin having a fluorene structure.

[0006] Patent Document 2 (Japanese Patent Application Laid-Open No. 2005-187661) describes a method for simply improving the refractive index by blending (mixing, adding) a sulfur-containing compound into a fluorene-containing polyester.

[0007] Patent Document 3 (WO 2021 / 220811) describes an optical member made of a thermoplastic resin containing a phenanthrene structure. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-241962 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-187661 [Patent Document 3] International Publication No. 2021 / 220811 Summary of the Invention [Problem to be solved by the invention]

[0009] However, the polycarbonate resin described in Patent Document 1 has a low refractive index and is not fully satisfactory. Furthermore, as described in Patent Document 2, blending a sulfur-containing compound with a fluorene-containing polyester improves the refractive index, but the addition of a low-molecular-weight component reduces thermal stability, and if the compatibility of the two blended components is poor, transparency decreases. Furthermore, thermoplastic resins containing a phenanthrene structure as described in Patent Document 3 have an improved refractive index compared to resins containing a fluorene structure as described in Patent Document 1 and Patent Document 2. However, with the recent trend toward lighter, thinner, shorter, and smaller products, there is a demand for resins that can achieve a higher refractive index.

[0010] The present invention has been made in view of the above circumstances, and provides a diol compound that can improve the refractive index of an optical resin, as well as an optical resin, a polycarbonate resin, and an optical molded article that have an improved refractive index and excellent transparency. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to improve the refractive index of optical resins, and as a result have found that the refractive index can be improved by using a diol compound represented by the following formula (1) as a structural unit of the optical resin, thereby completing the present invention.

[0012] According to the present invention, the following diol compound, optical resin, polycarbonate resin, and optical molded article are provided.

[0013] [1] A diol compound represented by the following general formula (1): [ka] (In general formula (1), Ar1 to Ar5 each independently represent a hydrocarbon group or a heterohydrocarbon group, a to e each independently represent 0 or an integer of 1 to 2, and o and p each independently represent an integer of 1 to 6.) [2] The diol compound according to [1] above, wherein a to e in the general formula (1) are all 0. [3] An optical resin containing a structural unit derived from the diol compound according to [1] or [2] above. [4] A polycarbonate resin containing a structural unit derived from the diol compound according to [1] or [2] above. [5] In the polycarbonate resin according to [4], A polycarbonate resin in which the content of structural units derived from the diol compound represented by general formula (1) in the polycarbonate resin is 5 mol % or more and 99 mol % or less, when the total of all structural units in the polycarbonate resin is 100 mol %. [6] The polycarbonate resin according to [4] or [5], A polycarbonate resin further comprising a structural unit derived from a diol compound represented by the following general formula (2): [ka] (In general formula (2), R1 to R4 each independently represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms; each A independently represents an alkylene group having 2 to 8 carbon atoms; and p and q each independently represent an integer of 1 to 8.) [7] The polycarbonate resin according to any one of [4] to [6], Polystyrene equivalent weight average molecular weight (Mw) is 1.5 x 10 3 Over 2.0 x 10 5 Polycarbonate resin, which is: [8] The polycarbonate resin according to any one of [4] to [7], A polycarbonate resin having a glass transition temperature of 80°C or higher and 190°C or lower as measured by a differential scanning calorimeter. [9] The polycarbonate resin according to any one of [4] to [8], A polycarbonate resin having a refractive index of 1.65 or more and 1.85 or less at 23°C and a wavelength of 589 nm.

[10] An optically molded article comprising the polycarbonate resin according to any one of [4] to [9] above.

[11] The optical molded article according to

[10] above, which is an optical lens.

[12] The optical molded product according to

[10] above, which is an optical film. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a diol compound capable of improving the refractive index of an optical resin, as well as an optical resin, a polycarbonate resin, and an optical molded article having an improved refractive index and excellent transparency. DETAILED DESCRIPTION OF THE INVENTION

[0015] The following describes an embodiment of the present invention. Note that unless otherwise specified, "-" between numbers in the text indicates "above" or "below."

[0016] [Diol compounds] The diol compound according to this embodiment will be described below: The diol compound according to this embodiment is a diol compound represented by general formula (1).

[0017] [ka]

[0018] In general formula (1), Ar1 to Ar5 each independently represent a hydrocarbon group or a heterohydrocarbon group, a to e each independently represent 0 or an integer of 1 to 2, and o and p each independently represent an integer of 1 to 6.

[0019] In general formula (1), Ar1 to Ar5 are each preferably independently selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic heterohydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic heterohydrocarbon group having 4 to 12 carbon atoms, and more preferably selected from the group consisting of an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aliphatic heterohydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic heterohydrocarbon group having 4 to 12 carbon atoms.

[0020] In general formula (1), the hydrocarbon groups or heterohydrocarbon groups of Ar1 to Ar5 are preferably selected from the group consisting of methyl, ethyl, n-propyl, methoxy, ethoxy, n-propyloxy, methoxymethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, o-phenylphenyl, m-phenylphenyl, p-phenylphenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 3-phenyl-2-pyridinyl, 4-phenyl-2-pyridinyl, and 5-phenyl-2-pyridinyl groups.

[0021] In general formula (1), it is preferable that a to e are each independently 0 or 1, and it is more preferable that a to e are all 0.

[0022] In general formula (1), o and p are each preferably independently an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably each independently 1 or 2, and even more preferably both o and p are 2. When o and p are within the above ranges, the heat resistance of the optical resin containing a structural unit derived from the diol compound represented by general formula (1) can be further improved.

[0023] Examples of the diol compound represented by general formula (1) include the following compounds.

[0024] [ka]

[0025] [ka]

[0026] The diol compound represented by general formula (1) is preferably 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol), 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(methane-1-ol), 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(propan-1-ol), or 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(butan-1-ol), and more preferably 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol).

[0027] [Method of producing diol compound] The diol compound according to this embodiment can be synthesized, for example, by the following production method A or production method B.

[0028] <Manufacturing method A> The diol compound according to this embodiment can be produced by the following steps (i) to (vii). Hereinafter, the method for producing a diol compound according to this embodiment will be specifically explained using a method for producing 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol), which is a diol compound represented by general formula (1) in which a to e are all 0 and o and p are both 2. Diol compounds according to this embodiment other than 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) can also be produced in the same manner by appropriately changing the substituents of the raw material compounds.

[0029] Step (i): 2-Methoxy-6-naphthaleneboronic acid is reacted with 2-bromobenzaldehyde in a solvent (e.g., toluene and water, tetrahydrofuran and water, dimethyl sulfoxide and water) in the presence of a base (e.g., sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate) and a palladium catalyst such as tetrakis(triphenylphosphine)palladium under Suzuki-Miyaura coupling conditions to produce 2-(6-methoxynaphthalen-2-yl)benzaldehyde.

[0030] [ka]

[0031] Step (ii): 2-(6-methoxynaphthalen-2-yl)benzaldehyde obtained in step (i) is reacted with potassium tert-butoxide, a base such as n-butyllithium, a Wittig reagent such as (methoxymethyl)triphenylphosphonium chloride, or a Horner-Emmons reagent in a solvent such as tetrahydrofuran to produce 2-methoxy-6-[2-(2-methoxyvinyl)phenyl]naphthalene.

[0032] [ka]

[0033] Step (iii): 2-Methoxy-6-[2-(2-methoxyvinyl)phenyl]naphthalene obtained in step (ii) is reacted with trifluoromethanesulfonic acid, bismuth triflate, or the like in a solvent such as 1,2-dichloroethane to produce 2-methoxychrysene.

[0034] [ka]

[0035] Step (iv): 2-Methoxychrysene obtained in step (iii) is reacted with a demethylating agent such as boron tribromide or hydrobromic acid in a solvent such as dichloromethane to produce 2-chrysenol.

[0036] [ka]

[0037] Step (v): 2-Chrysenol obtained in step (iv) is reacted with a copper catalyst such as di-μ-hydroxo-bis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride, manganese dioxide or graphene oxide in a solvent such as tetrahydrofuran to produce 1,1′-bicrysenol.

[0038] [ka]

[0039] Step (vi): 1,1'-Bichysenol obtained in step (v) is reacted with 2-(2-bromoethoxy)tetrahydro-2H-pyran in the presence of a base such as potassium carbonate and potassium iodide in a solvent such as N,N-dimethylformamide to produce 2,2'-bis[2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy]-1,1'-bicrysene.

[0040] Step (vii): 2,2'-bis[2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy]-1,1'-bicrysene obtained in step (vi) is hydrolyzed in a solvent such as methyl cellosolve under an acid catalyst such as concentrated hydrochloric acid to produce 2,2'-[1,1'-bicrysene-2,2'-diylbis(oxy)]bis(ethan-1-ol).

[0041] Instead of steps (i) to (iv), 2-chrysenol can also be produced by sulfonating chrysene and then subjecting it to alkaline decomposition.

[0042] Instead of steps (vi) and (vii), 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) can also be produced by reacting 1,1'-bicrysenol with a hydroxyethoxylating agent such as ethylene oxide, ethylene carbonate, or a haloethanol having a protected hydroxyl group.

[0043] The reaction temperature, reaction time, and the like in steps (i) to (vii) can be set under any conditions.

[0044] <Manufacturing method B> The diol compound according to this embodiment can be produced by the following steps (a) to (e). Hereinafter, the method for producing a diol compound according to this embodiment will be specifically explained using a method for producing 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol), which is a diol compound represented by general formula (1) in which a to e are all 0 and o and p are both 2. Diol compounds according to this embodiment other than 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) can also be produced in the same manner by appropriately changing the substituents of the raw material compounds.

[0045] Step (a): 6-Bromo-naphthol is reacted with iron(III) chloride hexahydrate in a solvent such as water to produce 6,6'-dibromo-1,1'-binaphthalene-2,2'-diol.

[0046] [ka]

[0047] Step (b): The 6,6'-dibromo-1,1'-binaphthalene-2,2'-diol obtained in step (a) is reacted with bromoethanol having a protecting group (e.g., tetrahydro-2H-pyranyloxy group or benzyl group) in the presence of a base such as potassium carbonate, potassium hydroxide, sodium carbonate, or sodium hydroxide in a solvent such as N,N-dimethylformamide to produce intermediate B-1 having a protecting group in the following formula (b).

[0048] [ka] In the above formula (b), LG represents a protecting group. Hereinafter, in this specification, LG in chemical formulas similarly represents a protecting group.

[0049] Step (c): Intermediate B-1 obtained in step (b) is reacted with 2-formylphenylboronic acid in a solvent (e.g., toluene and water, tetrahydrofuran and water, dimethyl sulfoxide and water) in the presence of a base (e.g., sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate) and a palladium catalyst such as tetrakis(triphenylphosphine)palladium to produce intermediate B-2 in the following formula (c).

[0050] [ka]

[0051] Step (d): Intermediate B-2 obtained in step (c) is reacted with potassium tert-butoxide, a base such as n-butylbutyllium, a Wittig reagent such as (methoxymethyl)triphenylphosphonium chloride, or a Horner-Emmons reagent in a solvent such as tetrahydrofuran to produce intermediate B-3 in the following formula (d).

[0052] [ka]

[0053] Step (e): The intermediate B-3 obtained in step (d) is reacted with trifluoromethanesulfonic acid, bismuth triflate, or the like in a solvent such as 1,1,1,3,3,3-hexafluoroisopropyl alcohol to produce 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol).

[0054] [ka]

[0055] The reaction temperature, reaction time, and other conditions in steps (a) to (e) can be arbitrarily selected.

[0056] [Optical resin] One aspect of the present invention is an optical resin containing a structural unit derived from a diol compound represented by general formula (1). Examples of optical resins containing a structural unit derived from a diol compound represented by general formula (1) include polyester resins, polyurethane resins, polycarbonate resins, and polyether resins.

[0057] The polyester resin can be obtained by reacting a diol compound represented by general formula (1) with an aromatic dicarboxylic acid (e.g., terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid) or an aliphatic dicarboxylic acid (e.g., oxalic acid, malonic acid, succinic acid).

[0058] The polyurethane resin can be obtained by reacting the diol compound represented by general formula (1) with an aromatic diisocyanate (e.g., toluylene diisocyanate, xylylene diisocyanate) or an aliphatic diisocyanate (e.g., pentamethylene diisocyanate, hexamethylene diisocyanate, cyclohexanedimethylene diisocyanate).

[0059] As will be described later, the polycarbonate resin can be obtained by reacting a diol compound represented by general formula (1) with a carbonate precursor such as a carbonic acid diester.

[0060] The polyether resin can be obtained by reacting a diol compound represented by general formula (1) with an aliphatic dihalogen compound (for example, dibromoethane, dibromopropane) in the presence of a base.

[0061] In these resins, the reactants other than the diol compound represented by general formula (1) may be used alone or in combination. It is also possible to polymerize the resin by using a diol compound other than the diol compound represented by general formula (1) in combination.

[0062] When a diol compound other than the diol compound represented by general formula (1) is used in combination, when the total of the diol compound represented by general formula (1) and the diol compound other than the compound represented by general formula (1) is taken as 100 mol%, the proportion of the compound represented by general formula (1) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more. The proportion of the compound represented by general formula (1) relative to the total of the diol compound represented by general formula (1) and the diol compound other than the compound represented by general formula (1) is preferably 99 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and even more preferably 70 mol% or less.

[0063] Here, examples of diol compounds other than the diol compound represented by general formula (1) 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-ethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-n-propylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, hydroxyethoxy)-3-n-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-sec-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-2-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-( 2-hydroxyethoxy)-3-(3-methylphenyl)phenyl]fluorene, bis[4-(2'-hydroxyethoxy)phenyl]sulfide, bis[4-(2'-hydroxyethoxy)-3-methylphenyl]sulfide, bis[4-(2'-hydroxyethoxy)phenyl]sulfone, bis[4-(2'-hydroxyethoxy)-3-methylphenyl]sulfone, bis[4-(2'-hydroxyethoxy)phenyl]sulfoxide, bis[4-(2'-hydroxyethoxy)phenyl]sulfoxide, bis(4-hydroxyphenyl)methane, bis(4-hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 4,4-dihydroxyphenyl-1,1-m-diisopropylbenzene;Bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2,2,2,2-tetrahydro-3,3,3,3-tetramethyl-1,1-spirobis[1H-indene]-6,6-diol; dihydroxyaryl ethers such as bis(4-hydroxyphenyl)ether and bis(4-hydroxy-3,5-dichlorophenyl)ether; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydrophenyl)fluorene, 9,9-bis(4-hydroxy ... 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene;ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,10-decanediol, diethylene glycol, tetraethylene glycol, norbornane dimethanol, decahydronaphthalenedimethanol, tricyclo[5.2.1.0; 2.6 ] decanedimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, and the like can be mentioned.

[0064] [Polycarbonate resin] The polycarbonate resin according to this embodiment is produced using the diol compound represented by general formula (1) according to this embodiment. The polycarbonate resin according to this embodiment has a structural unit derived from the diol compound represented by general formula (1), which is represented by formula (1p). Such a polycarbonate resin can provide an optical molded article with an improved refractive index. It can be suitably used as a material for optical lenses.

[0065] [ka]

[0066] In formula (1p), Ar1 to Ar5, a to e, and o and p have the same meanings as in general formula (1). In addition, preferred embodiments of formula (1p) are the same as those in general formula (1).

[0067] In the polycarbonate resin according to this embodiment, when the total of all structural units in the polycarbonate resin is taken as 100 mol%, the content of the structural unit (1p) derived from the diol compound represented by general formula (1) in the polycarbonate resin is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more. When the total of all structural units in the polycarbonate resin is taken as 100 mol%, the content of the structural unit (1p) derived from the diol compound represented by general formula (1) in the polycarbonate resin is preferably 99 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, and even more preferably 70 mol% or less.

[0068] It is preferable that the content of the structural unit (1p) derived from the diol compound represented by general formula (1) in the polycarbonate resin is at least the above lower limit, since this improves the refractive index of the polycarbonate resin according to this embodiment.It is preferable that the content of the structural unit (1p) derived from the diol compound represented by general formula (1) in the polycarbonate resin is at most the above upper limit, since this allows the glass transition temperature (Tg) and weight average molecular weight (Mw) of the polycarbonate resin according to this embodiment to be adjusted to appropriate ranges.

[0069] The polycarbonate resin according to this embodiment may further contain a structural unit derived from a diol compound other than the diol compound represented by general formula (1) used in the optical resin according to this embodiment.

[0070] In the polycarbonate resin according to this embodiment, the constituent unit derived from a diol compound other than the diol compound represented by general formula (1) is preferably a constituent unit represented by formula (2p) derived from a diol compound represented by general formula (2).

[0071] [ka]

[0072] In general formula (2), R1 to R4 each independently represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms; A each independently represents an alkylene group having 2 to 8 carbon atoms; and p and q each independently represent an integer of 1 to 8.

[0073] In general formula (2), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. In general formula (2), examples of the aryl group having 6 to 20 carbon atoms include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, etc.

[0074] In general formula (2), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an eicosyl group.

[0075] In the general formula (2), examples of the cycloalkyl group having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotridecyl group, a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, and a cycloeicosyl group.

[0076] In general formula (2), it is preferable that R1 to R4 are each independently selected from a hydrogen atom, an aryl group having 6 to 20 carbon atoms, and an alkyl group having 1 to 3 carbon atoms, it is more preferable that R1 to R4 are each independently selected from a hydrogen atom, an aryl group having 6 to 20 carbon atoms, and a methyl group, and it is even more preferable that R1 to R4 are a hydrogen atom.

[0077] In general formula (2), A represents an alkylene group having 2 to 8 carbon atoms, and examples thereof include a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, a 1,7-heptylene group, and a 1,8-octylene group. In general formula (2), A is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

[0078] In general formula (2), p and q are preferably each independently an integer of 1 to 4, more preferably each independently an integer of 1 to 2, and even more preferably both p and q are 1.

[0079] [ka]

[0080] In formula (2p), R1 to R4, A, p and q have the same meanings as in general formula (2). In addition, preferred embodiments of formula (2p) are the same as those in general formula (2).

[0081] In the polycarbonate resin according to this embodiment, when the total of all structural units in the polycarbonate according to this embodiment is taken as 100 mol%, the content of the structural unit (2p) derived from the diol compound represented by general formula (2) is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, and even more preferably 20 mol% or more. When the total of all structural units in the polycarbonate according to this embodiment is taken as 100 mol%, the content of the structural unit (2p) derived from the diol compound represented by general formula (2) is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, and even more preferably 80 mol% or less.

[0082] In the polycarbonate resin according to this embodiment, when the content of the structural unit (1p) derived from the diol compound represented by general formula (1) is taken as 1 mole, the content of the structural unit (2p) derived from the diol compound represented by general formula (2) is preferably 0.65 moles or more and 9.00 moles or less, more preferably 1.00 moles or more and 5.67 moles or less, and even more preferably 1.50 moles or more and 4.00 moles or less.

[0083] The polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin according to this embodiment is preferably 1.5 × 10 3 More preferably, 2.0 × 10 3 More preferably, 5.0 × 10 3 More preferably, 1.0 × 10 4 or more, and preferably 2.0×10 5 Less than or equal to 1.2 × 10 5 or less, more preferably 1.0 × 10 5 or less, more preferably 5.0 × 10 4 or less, more preferably 3.0 × 10 4 The following is the result.

[0084] It is preferable that the Mw is equal to or greater than the lower limit, since this can further prevent the resulting molded article from becoming brittle.It is also preferable that the Mw is equal to or less than the upper limit, since the melt viscosity becomes more appropriate, making it easier to remove the resin after production, and the flowability becomes better, making it easier to injection mold in a molten state.

[0085] The refractive index (nD) of the polycarbonate resin according to this embodiment at 23°C and a wavelength of 589 nm is preferably 1.65 or more, more preferably 1.66 or more, even more preferably 1.68 or more, still more preferably 1.70 or more, even more preferably 1.71 or more, and still more preferably 1.72 or more. The refractive index (nD) of the polycarbonate resin according to this embodiment at 23°C and a wavelength of 589 nm is preferably 1.85 or less, more preferably 1.82 or less, and still more preferably 1.81 or less.

[0086] When the polycarbonate resin according to this embodiment is used in injection molding, the glass transition temperature (Tg) measured by a differential scanning calorimeter is preferably 80°C or higher, more preferably 85°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 130°C or higher, even more preferably 150°C or higher, and preferably 190°C or lower, more preferably 180°C or lower, even more preferably 170°C or lower. A Tg of at least the lower limit mentioned above is preferred because it broadens the usable temperature range. A Tg of at most the upper limit mentioned above is preferred because it lowers the melting temperature of the resin, making it less likely for the resin to decompose or discolor. A Tg of at most the upper limit mentioned above can reduce the difference between the mold temperature and the glass transition temperature of the resin, even with a general-purpose mold temperature controller. This makes it easy to use and is therefore preferred in applications where strict surface precision is required for the product.

[0087] Furthermore, the polycarbonate resin according to this embodiment may contain additives such as antioxidants, mold release agents, ultraviolet absorbers, flowability modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, and antibacterial agents.

[0088] [Manufacturing method of polycarbonate resin] The polycarbonate resin according to this embodiment can be produced by using a compound represented by general formula (1) as a raw material. Specifically, the compound represented by general formula (1) and a carbonate precursor such as a carbonic acid diester are reacted by a melt polycondensation method in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst comprising both, or in the absence of a catalyst.

[0089] Examples of carbonate diesters used in the production of the polycarbonate resin according to this embodiment include diphenyl carbonate, di-p-tolyl carbonate, di-m-tolyl carbonate, di-o-tolyl carbonate, bis(p-chlorophenyl)carbonate, bis(m-chlorophenyl)carbonate, bis(o-chlorophenyl)carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is preferred. Diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 moles, more preferably 0.98 to 1.10 moles, per mole of the total of the diol compounds.

[0090] Examples of basic compound catalysts used in the production of the polycarbonate resin according to this embodiment include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds. Preferred examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides of alkali metal and alkaline earth metal compounds, as well as quaternary ammonium hydroxides and their salts, and amines. These compounds can be used alone or in combination.

[0091] Examples of alkali metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, or dilithium salt of bisphenol A, and sodium salt, potassium salt, cesium salt, or lithium salt of phenol.

[0092] Examples of alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specific examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

[0093] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specific examples include quaternary ammonium hydroxides having an alkyl group, an aryl group, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as n-propylamine and n-butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts such as ammonia, tetramethylammonium borohydride, tetra-n-butylammonium borohydride, tetra-n-butylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0094] As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used, and these can be used alone or in combination. Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, and lead(IV) acetate. These catalysts are used in an amount of 10 moles per mole of the total of the diol compounds. -9 ~10 -3 In terms of molar ratio, preferably 10 -7 ~10 -4 Used in molar ratios.

[0095] The melt polycondensation method uses the above-mentioned raw materials and catalyst to carry out melt polycondensation under heating at normal pressure or reduced pressure while removing by-products caused by an ester exchange reaction. In the melt polycondensation method according to this embodiment, it is desirable to melt the diol compound and the carbonate diester in a reaction vessel, and then carry out the reaction in a state in which the monohydroxy compound produced as a by-product remains.

[0096] In order to retain the monohydroxy compound, the pressure can be controlled by, for example, blocking the reaction apparatus or reducing or increasing the pressure. The reaction time for this step is preferably 20 minutes or more and 240 minutes or less, more preferably 40 minutes or more and 180 minutes or less, and even more preferably 60 minutes or more and 150 minutes or less. In this case, if the by-product monohydroxy compound is distilled off immediately after production, the final polycarbonate resin will have a low content of high molecular weight compounds. However, if the by-product monohydroxy compound is retained in the reaction vessel for a certain period of time, the final polycarbonate resin will have a high content of high molecular weight compounds.

[0097] Generally, melt polycondensation reactions are carried out in two or more stages. Specifically, the first stage reaction is carried out at a temperature of preferably 120 to 270°C, more preferably 180 to 240°C, under normal or elevated pressure, for preferably 0.1 to 5 hours, more preferably 0.5 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum of the reaction system to react the diol compound with the carbonate diester, and finally, the polycondensation reaction is preferably carried out at a reduced pressure of 133 Pa (1 mmHg) or less, at a temperature of 200 to 350°C, for 0.05 to 2 hours.

[0098] The melt polycondensation reaction may be carried out in a continuous manner or a batch manner. The reaction apparatus used for carrying out the reaction may be a vertical type equipped with an anchor-type impeller, a Maxblend impeller, a helical ribbon-type impeller, etc., a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, etc., or an extruder type equipped with a screw. In addition, it is preferable to use a reaction apparatus that is an appropriate combination of these reaction apparatuses, taking into consideration the viscosity of the polymer.

[0099] After the polycondensation reaction is complete, the catalyst may be removed or deactivated from the polycarbonate resin according to this embodiment in order to maintain thermal stability and hydrolytic stability. A commonly used method for deactivating the catalyst is to add a known acidic substance. Specific examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, di-n-octyl phosphite, and mono-n-octyl phosphite; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, di-n-butyl phosphate, and di-n-octyl phosphate. Suitable examples of suitable deactivators include phosphate esters such as mono-n-octyl phosphate; phosphonic acids such as diphenylphosphonic acid, di-n-octylphosphonic acid, and di-n-butylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acid and phenylboric acid; aromatic sulfonates such as tetra-n-butylphosphonium n-dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkyl sulfates such as dimethyl sulfate; and organic halides such as benzyl chloride. These deactivators are preferably used in an amount of 0.01 to 50 times, more preferably 0.3 to 20 times, the molar amount of the catalyst. Less than 0.01 times the molar amount of the catalyst is undesirably insufficient in deactivation effect. More than 50 times the molar amount of the catalyst is undesirably used because the heat resistance of the resin decreases and the molded product is more likely to be discolored.

[0100] After catalyst deactivation, a step of removing low-boiling compounds in the polymer by volatilization at a pressure of 13 to 133 Pa (0.1 to 1 mmHg) and a temperature of 200 to 350° C. A horizontal apparatus equipped with stirring blades with excellent surface renewal ability, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used for this step.

[0101] The polycarbonate resin according to this embodiment is desired to have as little foreign matter content as possible, and filtration of the molten raw material, filtration of the catalyst solution, etc. are preferably carried out. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the produced resin through a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the step of collecting resin pellets is preferably carried out in a low-dust environment, and a cleanliness level of class 1000 or less is more preferable.

[0102] [Optical molded object] The optical molded article according to this embodiment contains the polycarbonate resin according to this embodiment, and the optical molded article can be produced using the polycarbonate resin according to this embodiment. For example, molding can be performed by any method such as injection molding, compression molding, injection compression molding, extrusion molding, solution casting, or the like. The polycarbonate resin according to this embodiment has excellent moldability and heat resistance, and can be particularly advantageously used in optical lenses that require injection molding. During molding, the polycarbonate resin according to this embodiment can be mixed with other resins such as other polycarbonate resins and polyester resins.

[0103] The polycarbonate resin according to this embodiment exhibits a high refractive index, excellent heat resistance, and fluidity suitable for molding. Furthermore, because it has low birefringence and is less likely to cause optical distortion, it can be advantageously used as an optical molded article suitable for structural or functional materials for optical components such as transparent conductive substrates used in liquid crystal displays, organic EL displays, solar cells, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays, in addition to optical lenses.

[0104] The optically molded article obtained using the polycarbonate resin according to this embodiment preferably has a total light transmittance of 82% or more, more preferably 85% or more, measured in accordance with JIS K-7361-1 (1997).

[0105] Furthermore, various additives may be used to impart various properties to the extent that the object of this embodiment is not impaired. Examples of additives include antioxidants, processing stabilizers, mold release agents, ultraviolet absorbers, bluing agents, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, heat-shielding agents, fluorescent dyes (including fluorescent brighteners), pigments, light scattering agents, reinforcing fillers, surfactants, antibacterial agents, plasticizers, compatibilizers, other resins, elastomers, etc.

[0106] 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-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-hydroxyphenyl)propionate, tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-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 content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by mass relative to 100 parts by mass of the polycarbonate resin.

[0107] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers.

[0108] Examples of phosphorus-based heat-treatment stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tri-n-decyl phosphite, tri-n-octyl phosphite, tri-n-octadecyl phosphite, di-n-decyl monophenyl phosphite, di-n-octyl monophenyl phosphite, diisopropyl monophenyl phosphite, mono-n-butyl di ... diisopropyl monophenyl phosphite, mono-n-butyl diphenyl phosphite, diisopropyl monophenyl phosphite, diisopropyl monophenyl phosphite, mono-n-butyl diphenyl phosphite, diisopropyl monophenyl phos diphenyl phosphite, monodecyl diphenyl phosphite, mono n-octyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(n-nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert 2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tri-n-butyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, di-n-butyl phosphate, di-n-octyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by mass per 100 parts by mass of the polycarbonate resin.

[0109] Examples of sulfur-based processing heat stabilizers include pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-3,3′-thiodipropionate. The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by mass per 100 parts by mass of the polycarbonate resin.

[0110] Preferably, the release agent is one that comprises 90% by mass or more of an ester of an alcohol and a fatty acid. Specific examples of the ester of an alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial or complete ester of a polyhydric alcohol and a fatty acid. The ester of the monohydric alcohol and a fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Furthermore, the partial or complete ester of the polyhydric alcohol and a fatty acid is preferably a partial or complete ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

[0111] Examples of esters of monohydric alcohols and saturated fatty acids include stearyl stearate, palmityl palmitate, n-butyl stearate, methyl laurate, isopropyl palmitate, etc. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include full or partial esters of dipentaerythritol such as stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate.

[0112] The content of these release agents is preferably in the range of 0.005 to 2.0 parts by mass, more preferably in the range of 0.01 to 0.6 parts by mass, and even more preferably in the range of 0.02 to 0.5 parts by mass, relative to 100 parts by mass of the polycarbonate resin.

[0113] The ultraviolet absorber is preferably at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. The ultraviolet absorbers listed below may be used alone or in combination of two or more.

[0114] Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-n-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and the like.

[0115] Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0116] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(n-hexyl)oxy]-phenol and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(n-octyl)oxy]-phenol.

[0117] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).

[0118] Examples of cyanoacrylate ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0119] The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass, more preferably 0.02 to 1.0 part by mass, and even more preferably 0.05 to 0.8 parts by mass, relative to 100 parts by mass of the polycarbonate resin. If the blending amount is within this range, it is possible to impart sufficient weather resistance to the polycarbonate resin depending on the application.

[0120] Examples of bluing agents include Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthren Blue RLS from Clariant.

[0121] Bluing agents are effective in eliminating the yellow tinge of polycarbonate resin. In particular, weather-resistant polycarbonate resins contain a certain amount of UV absorbers, which tend to cause the polycarbonate resin molded products to take on a yellow tinge due to the "effect and color of the UV absorbers." Therefore, the addition of a bluing agent is particularly effective in imparting a natural transparency to sheets and lenses. The blending amount of the bluing agent is, for example, preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm, relative to the polycarbonate resin.

[0122] If necessary, a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical molded body. The antireflection layer may be a single layer or a multilayer, and may be made of either an organic or inorganic material, but is preferably made of an inorganic material. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0123] (optical lenses) Optical lenses manufactured using the polycarbonate resin according to this embodiment have a high refractive index and excellent heat resistance, making them extremely useful in fields where expensive high-refractive-index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. If necessary, they are preferably used in the form of aspherical lenses. Because aspherical lenses can essentially eliminate spherical aberration with a single lens, there is no need to eliminate spherical aberration by combining multiple spherical lenses, which allows for weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses. The optical lens according to this embodiment is molded by any method, such as injection molding, compression molding, injection compression molding, etc. This embodiment makes it possible to more easily obtain a high refractive index, low birefringence aspherical lens, which is technically difficult to process using glass lenses.

[0124] (Optical film) The optical film produced using the polycarbonate resin according to this embodiment has excellent transparency and heat resistance, and is therefore suitable for use as a film for liquid crystal substrates, optical memory cards, and the like.

[0125] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0126] The present embodiment will be described in detail below with reference to examples and comparative examples, but the present embodiment is not limited to the descriptions of these examples.

[0127] 1. Measurement and evaluation methods In the following examples and comparative examples, the measurement and evaluation of each physical property was carried out by the following methods.

[0128] 1) Weight average molecular weight (Mw) in terms of polystyrene: A calibration curve was prepared using a gel permeation chromatograph (GPC: Waters 1515, 2414, and 2489) with chloroform as the eluent and standard polystyrene of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, Mw was calculated from the GPC retention time. GPC equipment: Waters 1515, 2414 and 2489 GPC column: Shodex GPC K-806L Measurement temperature: 40℃ Sample concentration: 0.3 wt%

[0129] 2) Refractive index (nD): A 4.0 wt% solution of resin in chloroform was coated onto a silicon wafer using a spin coater at 800 rpm for 40 seconds and 1500 rpm for 10 seconds, and then baked at 120°C for 5 minutes to prepare a sample. Using a spectroscopic ellipsometer GES5E (manufactured by SEMILAB), the refractive index and film thickness of the film at 23°C and 589 nm were calculated by fitting the following optical model to the optical measurement data at 23°C and wavelengths of 200-1000 nm. (optical model) Layer structure: film / SiO2 (2 nm thick) / Si substrate (500 μm thick) Dispersion equation of film: Cauchy + Lorentz oscillator model

[0130] 3) Glass transition temperature (Tg): Measured using a differential scanning calorimeter (DSC: DSC-60 manufactured by Shimadzu Corporation) at a temperature rise rate of 10°C / min.

[0131] 4) Melting point: Measured visually using a differential scanning calorimeter (DSC: Shimadzu DSC-60) or a polarizing microscope (Olympus BX50) combined with a hot stage (Mettler Toledo HS-1).

[0132] 5) Copolymerization ratio: 1 The NMR of the resin dissolved in chloroform-d1 was measured using a H-NMR (JEOL Corporation, product name: JNM-ECZ400S), and the copolymerization ratio was calculated from the integral ratio of hydrogen bonded to aromatic carbon.

[0133] 6) Total light transmittance: For a 500 μm thick sheet made of polycarbonate resin produced in the examples, measurement was performed using a turbidity meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS K-7361-1.

[0134] 1. Preparation of the diol compound represented by formula (1) Example 1 Synthesis of 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) Step (i): Synthesis of 2-(6-methoxynaphthalen-2-yl)benzaldehyde To a mixture of 20.51 g (101.15 mmol) of 2-methoxy-6-naphthaleneboronic acid, 17.91 g (97.36 mmol) of 2-bromobenzaldehyde, 34.59 g (250.65 mmol) of potassium carbonate, 350 g of toluene, and 250 g of water was added 71.8 mg (0.1103 mmol) of dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II), and the mixture was stirred for 3 hours. The mixture was heated and stirred at 0°C. After cooling, the aqueous layer was separated, and the toluene layer was washed twice with distilled water. The toluene layer was separated and dried over magnesium sulfate. The toluene was removed from the toluene layer using a rotary evaporator, and methanol was added to the residue to obtain 22.15 g of the target 2-(6-methoxynaphthalen-2-yl)benzaldehyde. The yield was 87%, and the HPLC purity was 96.8 Area%. The melting point was 85.18°C.

[0135] Step (ii): Synthesis of 2-methoxy-6-[2-(2-methoxyvinyl)phenyl]naphthalene A suspension consisting of 32.15 g (93.79 mmol) of (methoxymethyl)triphenylphosphonium chloride and 100 mL of tetrahydrofuran was cooled to 2°C in an ice bath, and 100 mL of a 1.0 mol / L solution of potassium tert-butoxide in tetrahydrofuran was added thereto over 14 minutes. After stirring the reaction solution at 4°C for 15 minutes, a solution consisting of 15.30 g (58.37 mmol) of 2-(6-methoxynaphthalen-2-yl)benzaldehyde and 30 g of tetrahydrofuran was added dropwise over 15 minutes. The temperature of the reaction solution was raised to 10°C and then gradually decreased to 4°C. The mixture was then warmed to room temperature and stirred at the same temperature for 2 hours, after which the tetrahydrofuran was removed by distillation using a rotary evaporator. To the residue, 200 ml of toluene and 200 ml of distilled water were added and mixed. The aqueous layer was separated and washed twice with distilled water. The resulting toluene layer was dried over magnesium sulfate, and the toluene was removed using a rotary evaporator. The residue was purified by column chromatography (silica gel, eluent: chloroform / hexane = 3:2) to obtain 16.94 g of the desired 2-methoxy-6-[2-(2-methoxyvinyl)phenyl]naphthalene. Yield: 100%, HPLC purity: 98.5 Area%, melting point: 81.90 °C.

[0136] Step (iii): Synthesis of 2-methoxychrysene To a solution of 13.10 g (45.15 mmol) of 2-methoxy-6-[2-(2-methoxyvinyl)phenyl]naphthalene and 150 g of 1,2-dichloroethane, 1.03 g (1.57 mmol) of bismuth triflate was added and stirred overnight at room temperature. The precipitate was then filtered and washed with water. The filtrate was concentrated, and 200 mL of toluene and 200 mL of water were added. After washing with water, the toluene layer was washed twice with distilled water. The toluene layer was dried over magnesium sulfate and the toluene was removed using a rotary evaporator. Methanol was added to the residue to obtain 1.10 g of crystals. This was combined with the solid originally filtered and recrystallized from methyl cellosolve to obtain a total of 11.14 g of 2-methoxychrysene as a white solid. Yield: 96%, HPLC purity: 99.2 Area%, melting point: 254.86 °C.

[0137] Step (iv): Synthesis of 2-chrysenol 11.00 g (42.62 mmol) of 2-methoxychrysene was dissolved in 300 g of dichloromethane and cooled to 0°C in an ice bath. 67.86 g of a 1.0 mol / L solution of boron tribromide in dichloromethane was added dropwise over 20 minutes. The mixture was then stirred overnight until the temperature reached room temperature. After cooling again in an ice bath, an additional 20 g of a solution of boron tribromide in dichloromethane was added dropwise over 10 minutes. The mixture was poured into ice water, and the resulting solid was filtered and washed with water to obtain 4.94 g of 2-chrysenol as white crystals. Ethyl acetate was added to the filtrate, and after washing with water, the ethyl acetate layer was dried over magnesium sulfate and then distilled off using a rotary evaporator. Toluene and hexane (1:1) were added to the residue, and the resulting solid was filtered to obtain 4.87 g of 2-chrysenol as a brown solid. Yield: 96%, HPLC purity: 98.0 Area%. Melting point: 239-241°C.

[0138] Step (v): Synthesis of 1,1'-vicrysenol To a solution of 11.92 g (48.83 mmol) of 2-chrysenol and 261 g of tetrahydrofuran, 4.45 g of di-μ-hydroxo-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride was added, and the mixture was heated and stirred at 50°C for 5 days. The tetrahydrofuran was then removed using a rotary evaporator, and ethyl acetate was added. The insoluble matter was then filtered off. The resulting solid was washed twice with a 2N aqueous ammonia solution and then with water. After drying under reduced pressure at 60°C, the solid was suspended and washed twice with toluene to obtain 4.19 g of 1,1'-bicrysenol as a light brown solid. The filtrate from which the solid was removed was washed with a 2N aqueous ammonia solution and a 2N aqueous hydrochloric acid solution, followed by two washes with distilled water. The ethyl acetate layer was dried over magnesium sulfate, and the ethyl acetate was then removed using a rotary evaporator. Toluene was added to the residue, and the mixture was washed twice with toluene to obtain 5.92 g of 1,1'-vicrysenol. The yield was 85%, the HPLC purity was 95.7 Area%, and the melting point was 350°C or higher.

[0139] Step (vi): Synthesis of 2,2'-bis[2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy]-1,1'-bicrysene A mixture of 10.00 g (20.57 mmol) of 1,1'-bicrysenol, 8.28 g (60 mmol) of potassium carbonate, 9.41 g (45.23 mmol) of 2-(2-bromoethoxy)tetrahydro-2H-pyran, 1.26 g of potassium iodide, and 80 g of N,N-dimethylformamide was heated to 80°C and stirred for 16 hours. The N,N-dimethylformamide was then removed by distillation using a rotary evaporator, and 300 ml of toluene and 300 ml of water were added to the residue. The aqueous layer was separated and then washed twice with distilled water. The toluene layer was dried over magnesium sulfate, and the toluene was removed by distillation using a rotary evaporator. The residue was purified by column chromatography (silica gel: eluent: chloroform / ethyl acetate = 4:1) to obtain 13.21 g of the desired 2,2'-bis[2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy]-1,1'-bicrysene as colorless crystals. Yield: 89%, HPLC purity: 94.4 Area%, Melting point: 106°C.

[0140] Step (vii): Synthesis of 2,2′-[1,1′-bicrysen-2,2′-diylbis(oxy)]bis(ethan-1-ol) A mixture of 12.61 g (17.00 mmol) of 2,2'-bis[2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy]-1,1'-bicrysene and 80 g of methyl cellosolve was heated to 100°C to form a homogeneous solution, to which 2.72 g of concentrated hydrochloric acid was added and heated with stirring for 4 hours. The methyl cellosolve was then removed by distillation using a rotary evaporator, 200 g of distilled water was added to the residue, and the precipitate was filtered off. The resulting solid was suspended and washed twice in distilled water and then dried under reduced pressure at 60°C. The dried solid was suspended and washed twice in toluene, followed by extraction with heat using methyl cellosolve, and the methyl cellosolve was cooled to obtain 8.88 g of the target 2,2'-[1,1'-bicrysene-2,2'-diylbis(oxy)]bis(ethan-1-ol) as colorless crystals. 2,2'-[1,1'-Bichrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) is a diol compound represented by the general formula (1), where a to e are all 0, and o and p are all 2. The yield is 91%, and the HPLC purity is 99.2 Area%. The melting point is 334 to 337°C. 1 H-NMR(DMSO-d6)δ=3.24-3.49(m, 4H), 4.14(t, 4H), 4.61(t, 2H), 7.22(d, 2H), 7.56-7.68(m, 4 H), 7.82(d, 2H), 8.09(d, 2H), 8.15(d, 2H), 8.57(d, 2H), 8.71(d, 2H), 8.93(d, 2H), 9.11(d, 2H)

[0141] 2. Polycarbonate resin manufacturing Example 2 4.00 g (6.96 mmol) of 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) obtained in Example 1, 4.58 g (10.45 mmol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]-9H-fluorene, 3.80 g (17.75 mmol) of diphenyl carbonate, and 6 μL (1.2 × 10) of 0.02 M aqueous sodium hydrogen carbonate solution were mixed. -4(mmol) was charged into a reactor equipped with a distillation device and reacted at 270°C and 100 kPa for 1 hour. Thereafter, the degree of vacuum was adjusted to 22 kPa and the reaction was carried out for 20 minutes, and then the degree of vacuum was adjusted to 13 kPa and the reaction was carried out for 30 minutes. After that, the degree of vacuum was increased to 130 Pa over 40 minutes and the reaction was carried out at the same pressure for 30 minutes. When the predetermined torque was reached, the vacuum was released with nitrogen gas and the polycarbonate resin was extracted. The weight average molecular weight of the resulting polycarbonate resin was 15,300, and the Tg was 182°C. 1 The results of H-NMR revealed that this polycarbonate resin contained 40 mol % of the diol compound according to this embodiment, in which in general formula (1), a to e are all 0 and o and p are both 2. The refractive index nD of the polycarbonate resin was 1.6863.

[0142] Example 3 2.00 g (3.48 mmol) of 2,2'-[1,1'-bicrysen-2,2'-diylbis(oxy)]bis(ethan-1-ol) obtained in Example 1, 6.10 g (13.92 mmol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]-9H-fluorene, 3.80 g (17.75 mmol) of diphenyl carbonate, and 6 μL (1.2 × 10) of 0.02 M aqueous sodium hydrogen carbonate solution were mixed. -4 (mmol) was charged into a reactor equipped with a distillation device and reacted at 270°C and 100 kPa for 1 hour. Thereafter, the degree of vacuum was adjusted to 22 kPa and the reaction was carried out for 20 minutes, and then the degree of vacuum was adjusted to 13 kPa and the reaction was carried out for 30 minutes. After that, the degree of vacuum was increased to 130 Pa over 40 minutes and the reaction was carried out at the same pressure for 30 minutes. When the predetermined torque was reached, the vacuum was released with nitrogen gas and the polycarbonate resin was extracted. The weight average molecular weight of the resulting polycarbonate resin was 19,400 and the Tg was 161°C. 1 The results of H-NMR revealed that this polycarbonate resin contained 20 mol % of the diol compound according to this embodiment, in which a to e are all 0 and o and p are both 2 in general formula (1). The refractive index nD of the polycarbonate resin was 1.66 The total light transmittance of a 500 μm thick sheet of polycarbonate resin hot-pressed at 250° C. was 88%.

[0143] A linear approximation formula was calculated from the mole percentage of the diol compound in the polycarbonate resin obtained in Example 2 and Example 3, in which a to e are all 0 and o and p are both 2, and the refractive index nD of the polycarbonate resin. The refractive index nD of the homopolycarbonate resin of the diol compound according to this embodiment is 1.76 as a linear extrapolated value.

[0144] (Comparative Example 1) 8.25 g (17.4 mmol) of 10,10′-bis(2-hydroxyethoxy)-9,9′-biphenanthrene, 3.80 g (17.75 mmol) of diphenyl carbonate, and 6 μL (1.2 × 10) of 0.02 M sodium bicarbonate solution -4 (mmol) was charged into a reactor equipped with a distillation device and reacted at 270°C and 100 kPa for 1 hour. Thereafter, the degree of vacuum was adjusted to 22 kPa and the reaction was carried out for 20 minutes, and then the degree of vacuum was adjusted to 13 kPa and the reaction was carried out for 30 minutes. After that, the degree of vacuum was increased to 130 Pa over 40 minutes and the reaction was carried out at the same pressure for 30 minutes. When the predetermined torque was reached, the vacuum was released with nitrogen gas and the polycarbonate resin was extracted. The weight average molecular weight of the obtained polycarbonate resin was 15,100, and Tg was 160° C. The refractive index nD of this polycarbonate resin was 1.7110.

[0145] A comparison of the refractive index nD of the homopolycarbonate resin of Comparative Example 1 with the extrapolated value of the refractive index nD of the homopolycarbonate resin of the diol compound according to this embodiment calculated from the polycarbonate resins obtained in Examples 2 and 3 revealed that the refractive index of the polycarbonate resin can be improved by using the diol compound according to this embodiment.

[0146] The diol compound according to the present embodiment can improve the refractive index of the resulting polycarbonate resin even when the copolymerization ratio is low. By copolymerizing the diol compound with other diol compounds, the glass transition temperature (Tg) and weight average molecular weight (Mw) can be adjusted to appropriate ranges, thereby providing a polycarbonate resin with better moldability.

Claims

1. A diol compound represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), Ar １ ~Ar ５ each independently represents a hydrocarbon group or a heterohydrocarbon group, a to e are all 0, and o and p each independently represent an integer of 1 to 6.

2. An optical resin comprising a structural unit derived from the diol compound according to claim 1.

3. A polycarbonate resin comprising a structural unit derived from the diol compound according to claim 1.

4. The polycarbonate resin according to claim 3, A polycarbonate resin in which the content of structural units derived from the diol compound represented by general formula (1) in the polycarbonate resin is 5 mol % or more and 99 mol % or less, when the total of all structural units in the polycarbonate resin is 100 mol %.

5. The polycarbonate resin according to claim 3 or 4, A polycarbonate resin further comprising a structural unit derived from a diol compound represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms; each A independently represents an alkylene group having 2 to 8 carbon atoms; and each p and q independently represents an integer of 1 to 8.

6. The polycarbonate resin according to claim 3 or 4, Polystyrene equivalent weight average molecular weight (Mw) is 1.5 x 10 ３ Above 2.0 x 10 ５ Polycarbonate resin, which is:

7. The polycarbonate resin according to claim 3 or 4, A polycarbonate resin having a glass transition temperature of 80°C or higher and 190°C or lower as measured by a differential scanning calorimeter.

8. The polycarbonate resin according to claim 3 or 4, A polycarbonate resin having a refractive index of 1.65 or more and 1.85 or less at 23°C and a wavelength of 589 nm.

9. An optical molded article comprising the polycarbonate resin according to claim 3 or 4.

10. The optical molded article according to claim 9, which is an optical lens.

11. The optical molded product according to claim 9, which is an optical film.

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