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

Abstract

To provide a diol compound enabling improvement of refractive index in a resin, and to provide a resin, a polycarbonate resin, and an optical molded body with improved refractive index.SOLUTION: A diol compound represented by formula (1). The symbol W in the formula (1) represents a group selected from the group consisting of formula (W-1) and formula (W-2), the symbol * indicating a bonding site.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a diol compound, a 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. As a technology relating to optical resins, for example, the technology described in Patent Document 1 can be mentioned.

[0004] Patent Document 1 describes an optical lens made of a polycarbonate resin obtained by carbonate-bonding 90 to 5 mol % of a dihydroxy compound having a specific structure and 10 to 95 mol % of a dihydroxy compound having a specific structure using a carbonic acid diester, and describes that it is possible to provide an optical lens with a high refractive index and low birefringence that can be produced industrially by injection molding. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-241962 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a diol compound capable of improving the refractive index of a resin, as well as a resin, a polycarbonate resin, and an optical molded article having an improved refractive index. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the refractive index can be improved by including a diol compound represented by the following formula (1) as a structural unit of a resin, thereby completing the present invention. According to the present invention, there are provided the following diol compound, resin, polycarbonate resin and optical molded article.

[0008] [1] A diol compound represented by the following formula (1): [ka] (In the formula (1), a hydrogen atom bonded to a carbon atom may be replaced by an alkyl group having 1 to 10 carbon atoms or a heteroatom-containing alkyl group having 1 to 10 carbon atoms, and n's each independently represent an integer of 1 to 4, W represents a group selected from the group consisting of the following formula (W-1) and the following formula (W-2) (wherein * indicates a point of attachment), [ka] [ka] Ar 1 and Ar 2 are each independently an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents; X is one selected from the group consisting of O, S, NH, NY, and C═O, and Y is an alkyl group having 1 to 10 carbon atoms or an alkyl group containing a heteroatom having 1 to 10 carbon atoms. [2] The diol compound according to [1], wherein in the formula (1), W is the formula (W-1). [3] In the formula (1), W is the formula (W-1), and in the formula (W-1), Ar 1 and Ar 2 each independently represents a group selected from the group consisting of the following formula (a) and the following formula (b), and R 1 ~R 3 and each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroatom-containing alkyl group having 1 to 10 carbon atoms, a phenyl group, or a fluorine atom. [ka] [ka] [4] The diol compound according to [1], wherein in the formula (1), W is the formula (W-2), and in the formula (W-2), X is one selected from the group consisting of O, S, and C═O. [5] The diol compound according to any one of [1] to [4], wherein in the formula (1), each n is independently an integer of 1 or more and 3 or less. [6] A resin containing a structural unit derived from the diol compound according to any one of [1] to [5]. [7] A polycarbonate resin containing a structural unit derived from the diol compound according to any one of [1] to [5]. [8] The polycarbonate resin according to [7], wherein the content of the structural unit derived from the diol compound represented by formula (1) in the polycarbonate resin is 1 mol % or more and 99 mol % or less, when the total of all structural units in the polycarbonate resin is 100 mol %. [9] A polycarbonate resin containing structural units derived from one or more diol compounds selected from the group consisting of the following formulas (2), (3), and (4): [ka] [ka] [ka] (In the formulas (2), (3), and (4), the hydrogen atoms bonded to the carbon atoms may be replaced with alkyl groups having 1 to 10 carbon atoms or heteroatom-containing alkyl groups having 1 to 10 carbon atoms, and each m is independently an integer of 1 to 4.)

[10] The polycarbonate resin according to [9], wherein the total content of structural units derived from one or more diol compounds represented by the group consisting of formulas (2), (3), and (4) in the polycarbonate resin is 1 mol % or more and 99 mol % or less, when the total of all structural units in the polycarbonate resin is 100 mol %.

[11] Polystyrene equivalent weight average molecular weight (Mw) is 1.5 x 10 3 Over 2.0 x 10 5 The polycarbonate resin according to any one of [7] to

[10] below:

[12] The polycarbonate resin according to any one of [7] to

[11] , which has a glass transition temperature of 100° C. or higher and 190° C. or lower as measured by a differential scanning calorimeter.

[13] A polycarbonate resin according to any one of [7] to

[12] , having a refractive index nD of 1.70 or more and 1.95 or less at a temperature of 23°C and a wavelength of 589 nm.

[14] An optical molded article comprising the resin according to [6].

[15] An optically molded article comprising the polycarbonate resin according to any one of [7] to

[13] .

[16] The optical molded product according to

[14] or

[15] , which is an optical lens.

[17] The optical molded product according to

[14] or

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

[0009] According to the present invention, it is possible to provide a diol compound capable of improving the refractive index of a resin, as well as a resin, a polycarbonate resin, and an optical molded article having an improved refractive index. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below based on embodiments.

[0011] In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0012] <Diol compounds> The diol compound of the present embodiment is represented by the following formula (1).

[0013] [ka]

[0014] In formula (1), a hydrogen atom bonded to a carbon atom may be replaced by an alkyl group having 1 to 10 carbon atoms or a heteroatom-containing alkyl group having 1 to 10 carbon atoms, each n is independently an integer of 1 to 4, W represents a group selected from the group consisting of the following formula (W-1) and the following formula (W-2) (in the formula, * represents a point of attachment), and Ar 1 and Ar 2 are each independently an aromatic group or a heteroaromatic group that is unsubstituted or substituted with one or more substituents, X is one selected from the group consisting of O, S, NH, NY, and C═O, and Y is an alkyl group having 1 to 10 carbon atoms or an alkyl group containing a heteroatom having 1 to 10 carbon atoms.

[0015] [ka]

[0016] [ka]

[0017] From the viewpoint of further improving the refractive index, the hydrogen atom bonded to the carbon atom in formula (1) may be replaced preferably with an alkyl group having 1 to 4 carbon atoms or a heteroatom-containing alkyl group having 1 to 4 carbon atoms, and more preferably with a methyl group or a heteroatom-containing alkyl group having 1 carbon atom.

[0018] In formula (1), n's are each independently an integer of 1 or more and 4 or less, and from the viewpoint of further improving the refractive index, n's are each preferably independently an integer of 1 or more and 3 or less, more preferably n's are an integer of 1 or 2, and even more preferably n's are 2. Furthermore, in formula (1), n's are each preferably 2.

[0019] In formula (1), W represents a group selected from the group consisting of formula (W-1) and formula (W-2) above, and is preferably formula (W-1) from the viewpoint of facilitating production of the diol compound and further improving the refractive index.

[0020] In formula (1), when W is the above formula (W-1), Ar 1 and Ar 2 are each independently an aromatic group or a heteroaromatic group which is unsubstituted or substituted with one or more substituents, and from the viewpoint of further improving the refractive index, preferably Ar 1 and Ar 2 each independently represents a group selected from the group consisting of the following formula (a) and the following formula (b), and more preferably Ar 1 and Ar 2 is the group represented by (a) above.

[0021] [ka]

[0022] [ka]

[0023] In formula (1), when W is the above formula (W-1), Ar 1 and Ar 2 It is preferable that the embodiment does not include an embodiment in which is directly bonded. Furthermore, the formula (1) preferably excludes a diol compound represented by the formula (2) described below.

[0024] In formula (a) and formula (b), R 1 ~R 3 From the viewpoint of further improving the refractive index, preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroatom-containing alkyl group having 1 to 10 carbon atoms, a phenyl group, or a fluorine atom, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a heteroatom-containing alkyl group having 1 to 10 carbon atoms, even more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a heteroatom-containing alkyl group having 1 to 4 carbon atoms, even more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a heteroatom-containing alkyl group having 1 to 2 carbon atoms, and even more preferably a hydrogen atom.

[0025] In formula (1), when W is the above formula (W-2), in formula (W-2), X is one selected from the group consisting of O, S, NH, NY, and C═O. From the viewpoint of further improving the refractive index, X is preferably one selected from the group consisting of O, S, and C═O, more preferably one selected from the group consisting of O and S, and even more preferably X is O. Furthermore, when X is NY, Y is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms and containing a heteroatom. From the viewpoint of further improving the refractive index, Y is preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and containing a heteroatom, and more preferably Y is an alkyl group having 1 to 2 carbon atoms or an alkyl group having 1 to 2 carbon atoms and containing a heteroatom.

[0026] The diol compound of this embodiment is preferably 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-((((9H-xanthen-9-ylidene)methylene)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 3,3'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(propan-1-ol), 4,4'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(propan-1-ol), 2,2'-(((2,2-di(naphthalen-2-yl)ethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-(((2,2-di-p-tolylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-(((2,2-bis(4-ethylphenyl)ethene-1,1-diyl)bis(4,1 -phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-(((2,2-bis(4-methoxyphenyl)ethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-(((2,2-bis(3-methoxyphenyl)ethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 2,2'-(((2,2-bis(4-fluorophenyl)ethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol and 10-(bis(4-(2-hydroxyethoxy)phenyl)methylene)anthracen-9(10H)-one). These may be used alone or in combination of two or more.

[0027] From the viewpoint of further improving the refractive index, the molecular weight of the diol compound of the present embodiment is preferably 425 or more, more preferably 440 or more, even more preferably 450 or more, and preferably 1200 or less, more preferably 900 or less, even more preferably 700 or less. The molecular weight of the diol compound of the present embodiment is preferably 425 or more and 1200 or less, more preferably 440 or more and 900 or less, and even more preferably 450 or more and 700 or less, from the viewpoint of further improving the refractive index.

[0028] The diol compound of this embodiment can be synthesized, for example, according to the method of Example 1 or 2 described below.

[0029] [Method for producing diol compound represented by formula (1)] The diol compound of the present embodiment can be synthesized, for example, by the following steps (i) and (ii). Step (i): A THP-protected benzophenone derivative such as bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)methanone is prepared by treating a benzophenone such as 4,4'-dihydroxybenzophenone with a 2H-pyran such as 2-(2-bromoethoxy)tetrahydro-2H-pyran in a solvent (e.g., tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane) in the presence of a base (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium methoxyl, sodium ethoxyl, sodium t-butoxyl, potassium t-butoxyl, n-butyllithium).

[0030] Step (ii): A diarylmethane such as diphenylmethane is treated in a solvent (e.g., tetrahydrofuran, methyl cellosolve, toluene and water, tetrahydrofuran and water, tetrahydrofuran and methanol, tetrahydrofuran and ethanol, dimethyl sulfoxide and water) in the presence of a base (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, potassium hydride, sodium methoxyl, sodium ethoxyl, sodium t-butoxyl, potassium t-butoxyl, n-butyllithium), to which the THP-protected benzophenone derivative obtained in step (i), such as bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)methanone, is added and reacted to produce a tetraarylethylene precursor such as 2,2-diphenyl-1,1-bis(4-(2-((tetrahydro-2H-pyran-2-yl)).

[0031] Step (iii): The tetraarylethylene precursor, such as 2,2-diphenyl-1,1-bis(4-(2-((tetrahydro-2H-pyran-2-yl), obtained in step (ii), is treated with an acid (concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid, or pyridinium p-toluenesulfonate) in a solvent (e.g., toluene, methyl cellosolve, toluene and water, tetrahydrofuran and water, tetrahydrofuran and methanol, tetrahydrofuran and ethanol, or dimethyl sulfoxide and water) to produce the target compound of formula (1).

[0032] [resin] One aspect of this embodiment is a resin containing a structural unit derived from a diol compound represented by formula (1), and is preferably an optical resin. Here, examples of the resin containing a constitutional unit derived from a diol compound represented by formula (1) include one or more resins selected from the group consisting of polyester resins, polyurethane resins, polycarbonate resins and polyether resins.

[0033] The polyester resin can be obtained by reacting the diol compound represented by 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).

[0034] The polyurethane resin can be obtained by reacting the diol compound represented by formula (1) with an aromatic diisocyanate (e.g., toluylene diisocyanate, xylylene diisocyanate) or an aliphatic diisocyanate (e.g., pentamethylene diisocyanate, hexamethylene diisocyanate, cyclohexanedimethylene diisocyanate).

[0035] As will be described later, the polycarbonate resin can be obtained by reacting a diol compound represented by formula (1) with a carbonate precursor such as a carbonic acid diester.

[0036] The polyether resin can be obtained by reacting the diol compound represented by formula (1) with an aliphatic dihalogen compound (for example, dibromoethane, dibromopropane) in the presence of a base.

[0037] In these resins, the reactants other than the diol compound represented by 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 formula (1) in combination.

[0038] When a diol compound other than the diol compound represented by formula (1) is used in combination, when the total of the diol compound represented by formula (1) and the diol compound other than the diol compound represented by formula (1) is taken as 100 mol %, from the viewpoint of further improving the refractive index, the proportion of the diol compound represented by formula (1) 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, even more preferably 20 mol % or more, and 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. Furthermore, when a diol compound other than the diol compound represented by formula (1) is used in combination, when the total of the diol compound represented by formula (1) and the diol compound other than the diol compound represented by formula (1) is taken as 100 mol %, from the viewpoint of further improving the refractive index, the proportion of the diol compound represented by formula (1) is preferably 1 mol % or more and 99 mol % or less, more preferably 5 mol % or more and 90 mol % or less, even more preferably 10 mol % or more and 80 mol % or less, and still more preferably 20 mol % or more and 70 mol % or less.

[0039] Here, examples of diol compounds other than the diol compound represented by 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-iso ... bis[4-(2-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 ]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)phenyl]sulfoxide, bis[4-(2'-hydroxyethoxy)phenyl]sulfoxide, bis(4-hydroxyphenyl)methane, 2,2-bis(4- 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.

[0040] [Polycarbonate resin] One aspect of the polycarbonate resin of this embodiment contains a structural unit derived from a diol compound represented by formula (1). Such polycarbonate resin can realize an optical molded article with an improved refractive index, and as a result, can be suitably used as a material for optical lenses.

[0041] In the polycarbonate resin of the present embodiment, when the total of all structural units in the polycarbonate resin is taken as 100 mol%, the content of structural units derived from the diol compound represented by formula (1) in the polycarbonate resin is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and is preferably 99 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, even more preferably 60 mol% or less. Furthermore, in the polycarbonate resin of the present embodiment, when the total of all structural units in the polycarbonate resin is taken as 100 mol %, the content of structural units derived from the diol compound represented by formula (1) in the polycarbonate resin is preferably 1 mol % or more and 99 mol % or less, more preferably 5 mol % or more and 90 mol % or less, even more preferably 10 mol % or more and 80 mol % or less, even more preferably 20 mol % or more and 70 mol % or less, and even more preferably 40 mol % or more and 60 mol % or less.

[0042] When the content of the diol compound-derived structural unit represented by formula (1) in the polycarbonate resin is equal to or greater than the above lower limit, the refractive index of the polycarbonate resin of the present embodiment can be further improved. When the content of the diol compound-derived structural unit represented by formula (1) in the polycarbonate resin is equal to or less than the above upper limit, the glass transition temperature (Tg) and weight average molecular weight (Mw) of the polycarbonate resin of the present embodiment can be adjusted to more appropriate ranges.

[0043] Furthermore, one aspect of the polycarbonate resin of the present embodiment contains structural units derived from one or more diol compounds selected from the group consisting of the following formulas (2), (3), and (4): Such polycarbonate resin can realize an optical molded article with an improved refractive index, and as a result, can be suitably used as a material for optical lenses.

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] In the above formulas (2), (3), and (4), the hydrogen atoms bonded to the carbon atoms may be replaced with alkyl groups having 1 to 10 carbon atoms or heteroatom-containing alkyl groups having 1 to 10 carbon atoms, and m's are each independently an integer of 1 to 4.

[0048] In order to further improve the refractive index, the hydrogen atoms bonded to the carbon atoms in the above formulas (2), (3), and (4) may be replaced preferably with an alkyl group having 1 to 4 carbon atoms or a heteroatom-containing alkyl group having 1 to 4 carbon atoms, and more preferably with a methyl group or a heteroatom-containing alkyl group having 1 carbon atom. From the viewpoint of further improving the refractive index, m in the above formulas (2), (3), and (4) is preferably each independently an integer of 1 or more and 3 or less, more preferably an integer of 1 or 2, and even more preferably 2. Furthermore, it is even more preferable that m in all of formulas (2), (3), and (4) is 2.

[0049] In the polycarbonate resin of the present embodiment, when the total of all structural units in the polycarbonate resin is taken as 100 mol%, the total content of structural units derived from one or more diol compounds represented by formulas (2), (3), and (4) in the polycarbonate resin is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and is preferably 99 mol% or less, more preferably 90 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, even more preferably 60 mol% or less. Furthermore, in the polycarbonate resin of the present embodiment, when the total of all structural units in the polycarbonate resin is taken as 100 mol %, the total content of structural units derived from one or more diol compounds represented by formulas (2), (3), and (4) in the polycarbonate resin is preferably 1 mol % or more and 99 mol % or less, more preferably 5 mol % or more and 90 mol % or less, even more preferably 10 mol % or more and 80 mol % or less, even more preferably 20 mol % or more and 70 mol % or less, and even more preferably 40 mol % or more and 60 mol % or less.

[0050] When the total content of structural units derived from one or more diol compounds represented by formulas (2), (3), and (4) in the polycarbonate resin is at least the above-mentioned lower limit, the refractive index of the polycarbonate resin of this embodiment can be further improved.When the total content of structural units derived from one or more diol compounds represented by formulas (2), (3), and (4) in the polycarbonate resin is at most the above-mentioned upper limit, the glass transition temperature (Tg) and weight average molecular weight (Mw) of the polycarbonate resin of this embodiment can be adjusted to more appropriate ranges.

[0051] The polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin of the present embodiment is preferably 1.5 × 10 3 More preferably, 2.0 × 103 More preferably, 5.0 × 10 3 or more, 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. The polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin of the present embodiment is preferably 1.5×10 3 Over 2.0 x 10 5 Less than 2.0 × 10, more preferably 3 Over 1.0 x 10 5 or less, more preferably 5.0 × 10 3 Over 5.0 x 10 4 or less, more preferably 1.0 × 10 4 Over 3.0 x 10 4 The following is the result.

[0052] When the Mw is equal to or greater than the lower limit, the resulting molded article can be prevented from becoming brittle. When the Mw is equal to or less than the upper limit, the melt viscosity becomes more appropriate, making it easier to remove the resin after production, and the flowability is further improved, making it easier to injection mold in a molten state.

[0053] The refractive index nD of the polycarbonate resin of this embodiment at a temperature of 23°C and a wavelength of 589 nm is preferably 1.70 or more, more preferably 1.71 or more, even more preferably 1.73 or more, and even more preferably 1.75 or more, from the viewpoint of improving the refractive index of the obtained optical molded article, and is preferably 1.95 or less, more preferably 1.93 or less, even more preferably 1.90 or less, and even more preferably 1.87 or less, from the viewpoint of adjusting the obtained optical molded article. The refractive index nD of the polycarbonate resin of this embodiment at a temperature of 23°C and a wavelength of 589 nm is preferably 1.70 or more and 1.95 or less, more preferably 1.71 or more and 1.93 or less, even more preferably 1.73 or more and 1.90 or less, and still more preferably 1.75 or more and 1.87 or less.

[0054] The glass transition temperature (Tg) of the polycarbonate resin of the present embodiment, measured by a differential scanning calorimeter, is preferably 100°C or higher, more preferably 105°C or higher, more preferably 110°C or higher, even more preferably 115°C or higher, even more preferably 120°C or higher, and even more preferably 125°C or higher, and is preferably 190°C or lower, more preferably 180°C or lower, even more preferably 170°C or lower, even more preferably 160°C or lower, even more preferably 150°C or lower, and even more preferably 140°C or lower. The glass transition temperature (Tg) of the polycarbonate resin of the present embodiment, measured by a differential scanning calorimeter, is preferably 100°C or higher and 190°C or lower, more preferably 105°C or higher and 180°C or lower, more preferably 110°C or higher and 170°C or lower, even more preferably 115°C or higher and 160°C or lower, even more preferably 120°C or higher and 150°C or lower, and even more preferably 125°C or higher and 140°C or lower. A Tg of at least the lower limit is preferable because the usable temperature range is wider. A Tg of at most the upper limit is preferable because the melting temperature of the resin is lower, making it less likely for the resin to decompose or discolor. A Tg of at most the upper limit can reduce the difference between the mold temperature and the glass transition temperature of the resin, even with a general-purpose mold temperature controller. Therefore, this is preferable because it is easy to use in applications where strict surface precision is required for the product.

[0055] Furthermore, the polycarbonate resin of the present 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.

[0056] [Manufacturing method of polycarbonate resin] The polycarbonate resin of this embodiment can be produced by using the diol compound represented by formula (1) as a raw material. Specifically, the polycarbonate resin can be produced by reacting the diol compound represented by formula (1) and a carbonate precursor such as a carbonic acid diester 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.

[0057] Examples of carbonate diesters used in the production of the polycarbonate resin of 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 0.30 to 0.80 moles, more preferably 0.40 to 0.70 moles, and even more preferably 0.45 to 0.60 moles, per mole of the diol compound represented by formula (1) and the diol compound other than the diol compound represented by formula (1).

[0058] Examples of basic compound catalysts used in producing the polycarbonate resin of 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 salts thereof, and amines. These compounds can be used alone or in combination.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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 preferably used in an amount of 10 moles per mole of the total of the diol compound represented by formula (1) and the diol compound other than the diol compound represented by formula (1). -9 ~10 -3 More preferably, the molar ratio is 10 -8 ~10 -4 Used in molar ratios.

[0063] 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 of 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 by-produced monohydroxy compound remains.

[0064] In order to retain the monohydroxy compound, the pressure can be controlled by blocking the reaction vessel or by reducing or increasing the pressure. The reaction time for this step is preferably 20 to 240 minutes, more preferably 30 to 180 minutes, and even more preferably 50 to 150 minutes. 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.

[0065] 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 250°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.

[0066] 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.

[0067] After the polycondensation reaction is complete, the catalyst may be removed or deactivated from the polycarbonate resin of 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.

[0068] 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.

[0069] The polycarbonate resin of 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 process of collecting resin pellets is naturally preferably carried out in a low-dust environment, and more preferably has a cleanliness level of Class 1000 or less.

[0070] Furthermore, when the polycarbonate resin of the present embodiment is produced using one or more diol compounds selected from the group consisting of formulas (2), (3), and (4) as raw materials, it can be produced in the same manner as when the compound represented by formula (1) is used as a raw material.

[0071] [Optical molded object] The optical molded article of this embodiment contains the resin of this embodiment or a polycarbonate resin, and the optical molded article can be manufactured using the resin of this embodiment or a polycarbonate resin. 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 resin or polycarbonate resin of this embodiment has excellent moldability and heat resistance, and can be used particularly advantageously in optical lenses that require injection molding. During molding, the resin or polycarbonate resin of this embodiment can be mixed with other resins such as other polycarbonate resins or polyester resins.

[0072] The resin or polycarbonate resin of this embodiment has an improved refractive index, and therefore can be advantageously used as an optical molded article suitable for structural or functional material applications for optical components such as transparent conductive substrates used in liquid crystal displays, organic EL displays, solar cells, etc., optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays, in addition to optical lenses.

[0073] Furthermore, in order to impart various properties to the optical molded article of this embodiment without impairing the object of this embodiment, various additives can be contained in the optical molded article of this embodiment. 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 and elastomers, etc.

[0074] 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 optical molded body of this embodiment is preferably 0.001 to 0.3 parts by mass relative to 100 parts by mass of the resin of this embodiment or the polycarbonate resin.

[0075] Examples of the processing stabilizer include phosphorus-based processing heat stabilizers and sulfur-based processing heat stabilizers.

[0076] 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 tert-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 optical molded product of this embodiment is preferably 0.001 to 0.2 parts by mass relative to 100 parts by mass of the resin of this embodiment or the polycarbonate resin.

[0077] 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 optical molded product of this embodiment is preferably 0.001 to 0.2 parts by mass per 100 parts by mass of the resin of this embodiment or the polycarbonate resin.

[0078] 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.

[0079] 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.

[0080] The content of the release agent in the optical molded body of this embodiment 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, per 100 parts by mass of the resin of this embodiment or the polycarbonate resin.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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).

[0086] 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.

[0087] The content of the ultraviolet absorber in the optical molded product of this embodiment 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 resin or polycarbonate resin of this embodiment. If the blending amount is within this range, it is possible to impart sufficient weather resistance to the resin or polycarbonate resin of this embodiment depending on the application.

[0088] Examples of bluing agents include Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthren Blue RLS from Clariant.

[0089] 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, and more preferably 0.1 to 1.2 ppm, relative to the resin of this embodiment or the polycarbonate resin.

[0090] 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.

[0091] [Optical Lenses] An optical molded article containing the resin or polycarbonate resin of this embodiment may be formed into an optical lens. The optical lens manufactured using the resin or polycarbonate resin of this embodiment has an improved refractive index, making it extremely useful for applications such as telescopes, binoculars, and television projectors, where expensive high-refractive-index glass lenses have traditionally been used. If necessary, it is preferable to use it in the form of an aspherical lens. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which enables weight reduction and reduced production costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses. The optical lens of 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.

[0092] [Optical film] The optical molded article containing the resin of this embodiment or the polycarbonate resin may be made into an optical film. The optical film produced using the resin of this embodiment or the polycarbonate resin has an improved refractive index and is therefore suitable for use as a film for a liquid crystal substrate, an optical memory card, etc.

[0093] 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]

[0094] 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.

[0095] In the following examples and comparative examples, the measurement and evaluation of each physical property was carried out by the following methods.

[0096] 1) Weight-average molecular weight (Mw) in polystyrene equivalent: A calibration curve was prepared using a gel permeation chromatograph (GPC: Waters 1515, 2414, and 2489) with chloroform as the eluent and standard polystyrene (product name: EasiCal Type PS-1, manufacturer: Agilent Technologies) of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, the Mw of each polycarbonate resin 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%

[0097] 2) Refractive index (nD): A chloroform solution of 4.0 wt% polycarbonate resin from each example was coated onto a silicon wafer using a spin coater at 800 rpm for 40 seconds and 1500 rpm for 10 seconds, and the sample was then baked at 120°C for 5 minutes to prepare the sample. Using a spectroscopic ellipsometer GES5E (manufactured by SEMILAB), the refractive index nD of the film at a temperature of 23°C and a wavelength of 589 nm was 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

[0098] 3) Glass transition temperature (Tg): Measured using a differential scanning calorimeter (DSC: Shimadzu DSC-60). The polycarbonate resin of each example was heated from room temperature to 250°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then cooled to -20°C at a heating rate of 10°C / min, held at that temperature for 5 minutes. The glass transition temperature Tg (°C) of each polycarbonate resin was determined from the endothermic curve obtained when the temperature was raised to 250°C at a heating rate of 10°C / min.

[0099] 4) Copolymerization ratio: 1 The NMR of each polycarbonate resin dissolved in chloroform-d1 was measured using a H-NMR (JEOL product name: JNM-ECZ400S), and the copolymerization ratio was calculated from the integral ratio of hydrogen bonded to aromatic carbon.

[0100] <Preparation of Diol Compound Represented by Formula (1)>

[0101] [Example 1]

[0102] Synthesis of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) Process (i) A 1 L four-neck flask equipped with a stirrer, reflux condenser, and thermometer was charged with 75.0 g (350.1 mmol) of 4,4'-dihydroxybenzophenone, 159.6 g (763.2 mmol) of 2-(2-bromoethoxy)tetrahydro-2H-pyran, 145.2 g (1050.3 mmol) of potassium carbonate, and 225 mL of DMF, and the mixture was stirred at 100 °C for 6 hours. The mixture was then cooled to room temperature, and 200 mL of water and 300 mL of ethyl acetate were added to separate the layers. 300 mL of ethyl acetate was added to the aqueous layer, and the combined organic layers were washed three times with 100 mL of saturated aqueous sodium chloride solution. The mixture was then concentrated using a rotary evaporator to obtain a solid. The obtained solid was dissolved in toluene and purified using a silica gel column to obtain 121.4 g (190.1 mmol) of bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)methanone (a compound represented by the following formula (1-i)) in a yield of 54%.

[0103] [ka]

[0104] The NMR analysis results of bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)methanone are shown below. 1 H-NMR (CDCl3): δ=1.48-1.91(m,12H), 3.50-3.58(m,2H), 3.80-3.95(m,4H), 4.05-4.13(m,2H), 4.19-4.29(m,4H), 4.72(t,2H), 6.99(d,4H), 7.77(d,4H)

[0105] Process (ii) A 1 L four-neck flask equipped with a stirrer, a dropping funnel, and a thermometer was charged with 28.5 g (169.6 mmol) of diphenylmethane and 130 ml of THF, cooled with ice, and then 103.6 mL (165.8 mmol) of n-butyllithium was added and stirred at the same temperature for 1 hour. Thereafter, a solution of 60.0 g (127.5 mmol) of (bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)methanone obtained in the above step (i) in THF (90 ml) was added dropwise, and the mixture was warmed to room temperature and stirred for 15 hours. Thereafter, the reaction mixture was ice-cooled, and 50 ml of a 5% aqueous ammonium chloride solution and 200 ml of ethyl acetate were added, followed by separation and washing twice with 100 ml of water. Thereafter, the mixture was concentrated using a rotary evaporator to obtain 86.2 g of a crude product of 2,2-diphenyl-1,1-bis(4-(2-((tetrahydro-2H-pyran-2-yl)) (a compound represented by the following formula (1-ii)).

[0106] [ka]

[0107] Process (iii) In a 1 L four-neck flask equipped with a stirrer, a Dean-Stark tube, a reflux condenser, and a thermometer, 86.2 g of the crude product of 2,2-diphenyl-1,1-bis(4-(2-(tetrahydro-2H-pyran-2-yl)) obtained in step (ii) above, 321 mg (1.28 mmol) of pyridinium p-toluenesulfonate, and 240 ml of toluene were placed and stirred at 120°C for 1 hour. The mixture was then concentrated using a rotary evaporator to give a solution of methanol. 700 ml of ethyl acetate was added and the mixture was stirred at 70°C for 2 hours. The mixture was then concentrated using a rotary evaporator, and 500 ml of ethyl acetate and 200 ml of water were added and the layers were separated. The mixture was then concentrated using a rotary evaporator to obtain a solid. The obtained solid was recrystallized with toluene to obtain 44.8 g (99.0 mmol) of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (a compound represented by the following formula (1-iii)), with a combined yield of 78% for steps (ii) and (1-iii). The molecular weight of compound (1-iii) was 452.55.

[0108] [ka]

[0109] The NMR analysis results of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) are shown below. 1 H-NMR (CDCl3): δ=2.03(t,2H), 3.88-3.94(m,4H), 4.00(t,4H), 6.61-6.67(m,4H), 6.90-6.96(m,4H), 6.98-7.14(m,10H)

[0110] [Example 2] Synthesis of 2,2'-((((9H-xanthen-9-ylidene)methylene)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol)

[0111] Process (i) Synthesis was carried out in the same manner as in steps (i) and (ii) of Example 1, except that 2.58 g (14.1 mmol) of xanthene was used as a starting material instead of diphenylmethane in step (ii), to obtain 6.4 g of a crude product of bis(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)(9H-xanthen-9-yl)methanol (a compound represented by the following formula (2-i)).

[0112] [ka]

[0113] Process (ii) The synthesis was carried out in the same manner as in step (iii) of Example 1, except that 6.4 g of the crude product of (4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)(9H-xanthen-9-yl)methanol obtained in step (i) above was used instead of 2,2-diphenyl-1,1-bis(4(2-tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)ethan-1-ol as the starting material. 2,2'-((((9H-xanthen-9-ylidene)methylene)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (a compound represented by formula (2-ii) below) was obtained in a two-step yield of 4.2 g (9.0 mmol). The molecular weight of compound (2-ii) was 466.53.

[0114] [ka]

[0115] The NMR analysis results of 2,2'-((((9H-xanthen-9-ylidene)methylene)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) are shown below. 1H-NMR (CDCl3): δ=2.04(t,2H), 3.90-3.97(m,4H), 4.05(t,4H), 6.69-6.75(m,2H), 6.78-6.84(m,4H), 6.90-6.97(m,2H), 7.11-7.18(m,8H)

[0116] <Preparation of polycarbonate resin containing structural units derived from diol compound represented by formula (1)>

[0117] [Example 3] 13.6 g (30.0 mmol) of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) obtained in Example 1, 6.62 g (30.9 mmol) of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), and 30 μL (6 × 10 -7 mol) was charged into a reactor equipped with a distillation device and reacted at 220°C and 100 kPa for 1 hour. Thereafter, the degree of vacuum was adjusted to 19 kPa and the reaction was continued for 20 minutes, followed by 70 minutes of reaction at the same temperature and pressure. Next, the degree of vacuum was adjusted to 16 kPa and the reaction was continued for 20 minutes, and then the degree of vacuum was adjusted to 13 kPa and the reaction was continued for 20 minutes. After that, the degree of vacuum was increased to 130 Pa over 40 minutes and the reaction was continued for 30 minutes at the same pressure. When the torque became constant at a predetermined value, the vacuum was released with nitrogen gas and the polycarbonate resin was extracted. The weight average molecular weight (Mw) of the obtained polycarbonate resin was 36,100, and the Tg was 129.5°C. The refractive index nD of this polycarbonate resin was 1.7586.

[0118] [Example 4] Instead of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 3.73 g (8.00 mmol) of 2,2'-((((9H-xanthen-9-ylidene)methylene)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) obtained in Example 2 was used, and 1.77 g (8.24 mmol) of DPC and 8 μL (2 × 10) of 0.02 M aqueous sodium bicarbonate solution were added. -7 A polycarbonate resin was produced according to the procedure described in Example 3, except that 1,2-dimethyl-2,4-dichloro-1,4-dichloro-2 ... The weight average molecular weight (Mw) of the obtained polycarbonate resin was 63,600, and the Tg was 124.1°C. The refractive index nD of this polycarbonate resin was 1.7287.

[0119] [Comparative Example 1] Instead of 2,2'-(((2,2-diphenylethene-1,1-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol), 4.39 g (10.0 mmol) of 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol) (a compound represented by the following formula (X)) was used, and 2.21 g (10.3 mmol) of DPC and 8 μL (2 × 10) of 0.02 M sodium bicarbonate aqueous solution were added. -7 A polycarbonate resin was prepared according to the procedure described in Example 3, except that 1,2-dimethyl-3-pyrrolidone (2,4-dichloro-1,2-diphenyl-2,4 ... The weight average molecular weight (Mw) of the obtained polycarbonate resin was 35,200, and the Tg was 145.3°C. The refractive index nD of this polycarbonate resin was 1.6431.

[0120] [ka]

Claims

1. A diol compound represented by the following formula (1): 【Chemical 1】 (In the formula (1), a hydrogen atom bonded to a carbon atom may be replaced by an alkyl group having 1 to 10 carbon atoms or a heteroatom-containing alkyl group having 1 to 10 carbon atoms; n's each independently represent an integer of 1 to 4; W represents a group selected from the group consisting of the following formula (W-1) and the following formula (W-2) (wherein * indicates a point of attachment), 【Chemistry 2】 【Chemistry 3】 Ar １ and Ar ２ are each independently an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents; X is one selected from the group consisting of O, S, NH, NY, and C═O, and Y is an alkyl group having 1 to 10 carbon atoms or an alkyl group containing a heteroatom having 1 to 10 carbon atoms.

2. The diol compound according to claim 1, wherein in the formula (1), W is the formula (W-1).

3. In the formula (1), W is the formula (W-1), and in the formula (W-1), Ar １ and Ar ２ each independently represents a group selected from the group consisting of the following formula (a) and the following formula (b), R １ ~R ３ and each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a heteroatom-containing alkyl group having 1 to 10 carbon atoms, a phenyl group, or a fluorine atom. 【Chemistry 4】 【Chemistry 5】

4. The diol compound according to claim 1, wherein in formula (1), W is formula (W-2), and in formula (W-2), X is one selected from the group consisting of O, S, and C═O.

5. The diol compound according to any one of claims 1 to 4, wherein in the formula (1), each n is independently an integer of 1 or more and 3 or less.

6. A resin comprising a structural unit derived from the diol compound according to any one of claims 1 to 5.

7. A polycarbonate resin comprising a structural unit derived from the diol compound according to any one of claims 1 to 5.

8. 8. The polycarbonate resin according to claim 7, wherein, when the total amount of all structural units in the polycarbonate resin is 100 mol%, the content of the structural unit derived from the diol compound represented by formula (1) in the polycarbonate resin is 1 mol% or more and 99 mol% or less.

9. A polycarbonate resin containing structural units derived from one or more diol compounds selected from the group consisting of the following formulas (2), (3), and (4): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In the formulas (2), (3), and (4), the hydrogen atom bonded to the carbon atom may be replaced with an alkyl group having 1 to 10 carbon atoms or a heteroatom-containing alkyl group having 1 to 10 carbon atoms, and each m is independently an integer of 1 to 4.)

10. 10. The polycarbonate resin according to claim 9, wherein, when the total of all structural units in the polycarbonate resin is taken as 100 mol%, the total content of structural units derived from one or more diol compounds represented by formulas (2), (3), and (4) in the polycarbonate resin is 1 mol% or more and 99 mol% or less.

11. Polystyrene equivalent weight average molecular weight (Mw) is 1.5 x 10 ３ Above 2.0 x 10 ５ The polycarbonate resin according to any one of claims 7 to 10, wherein:

12. The polycarbonate resin according to any one of claims 7 to 11, which has a glass transition temperature of 100°C or higher and 190°C or lower as measured by a differential scanning calorimeter.

13. 13. The polycarbonate resin according to claim 7, wherein the refractive index nD at a temperature of 23° C. and a wavelength of 589 nm is 1.70 or more and 1.95 or less.

14. An optical molded article comprising the resin according to claim 6.

15. An optical molded article comprising the polycarbonate resin according to any one of claims 7 to 13.

16. The optical molded article according to claim 14 or 15, which is an optical lens.

17. The optical molded product according to claim 14 or 15, which is an optical film.

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