Cyclic diol compound, method for producing the compound and use of the compound

Abstract

The present invention provides a cyclic diol compound useful as a resin raw material for polyester resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethacrylate resin, polyester polyol resin, etc. and a modifier for these resins, or a method for producing the same. The present invention relates to a compound represented by general formula (1), a method for producing the same, or a use thereof. [In the formula, R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d). (In formulas (a) to (d), the wavy line represents a bonding site. R 2 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms. )]

Description

Technical Field

[0001] The present invention relates to a cyclic diol compound, a method for producing the compound and uses of the compound. Background Art

[0002] Various cyclic diol compounds are known as resin raw materials for polyester resins and polycarbonate resins. Industrially available cyclic diol compounds include 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), etc. In addition, various cyclic diol compounds corresponding to the use of the resin to be produced have been reported.

[0003] For example, regarding polycarbonate resins for optical applications (e.g., optical lenses), there has been reported a method for producing polycarbonate resins using a diol component containing a specific aromatic diol compound having a fluorene ring structure for the purpose of reducing coloration and improving the optical properties of the resin such as transparency (Patent Document 1). In addition, there has been reported a method for producing polycarbonate resins using a specific fluorene-containing dihydroxy compound and other dihydroxy compounds in a specific ratio (Patent Document 2).

[0004] However, the properties of resins such as polyester resins and polycarbonate resins vary depending on the application fields in which the resins are used, and cyclic diol compounds that can satisfy the resin properties required in these fields are being sought. In particular, when the resin is used for optical purposes, cyclic diol compounds that can improve the optical properties of the resin are required.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-214803

[0008] Patent Document 2: Japanese Patent Application Publication No. 2013-001867 Summary of the invention

[0009] Problems to be solved by the invention

[0010] An object of the present invention is to provide a cyclic diol compound useful as a resin raw material and resin modifier for polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, polyester polyol resins, etc., and a method for producing the same.

[0011] Methods used to solve problems

[0012] The present inventors conducted intensive research to solve the above-mentioned problems and found that cyclic diol compounds having a special diacetal (dispiro) structure are compounds that have not been recorded in the literature and are useful as resin raw materials (monomers) for polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, polyester polyol resins, etc., and as resin modifiers for these resins. The present invention was completed based on this finding.

[0013] That is, the present invention provides the following cyclic diol compound, a method for producing the compound, and uses of the compound.

[0014] [Item 1]

[0015] The compound represented by the general formula (1) (hereinafter also referred to as "the cyclic diol compound of the present invention").

[0016]

[0017] [Where R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d).

[0018]

[0019] (In formulas (a) to (d), the wavy lines represent bonding sites. R 2 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms. )]

[0020] [Item 2]

[0021] The compound according to [Item 1], wherein in the general formula (1), R 1 are the same or different and are each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.

[0022] [Item 3]

[0023] The compound according to [Item 1] or [Item 2], wherein in the general formula (1), R 1 The same or different, each is methyl or ethyl.

[0024] [Item 4]

[0025] The compound according to any one of [Item 1] to [Item 3], wherein in the general formula (1), among the groups represented by the general formulas (a) to (d) represented by X, R 2The same or different groups are each a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

[0026] [Item 5]

[0027] The compound according to any one of [Item 1] to [Item 4], wherein in the general formula (1), R 1 is methyl or ethyl, X is a group represented by general formula (a), (c) or (d), R 2 are the same or different and are each a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a methoxy group or an ethoxy group.

[0028] [Item 6]

[0029] The compound according to any one of [Item 1] to [Item 5], wherein in the general formula (1), X is a phenyl group, a biphenyl group, a 1-naphthyl group or a 2-naphthyl group.

[0030] [Item 7]

[0031] The compound according to any one of [Item 1] to [Item 6], wherein in the general formula (1), X is a phenyl group.

[0032] [Item 8]

[0033] A monomer for a polyester resin, a polycarbonate resin, a polyurethane resin or a polyester polyol resin, comprising the compound described in any one of [Item 1] to [Item 7].

[0034] [Item 9]

[0035] A resin modifier for a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylate resin, a polymethacrylate resin or a polyester polyol resin, comprising the compound described in any one of [Item 1] to [Item 7].

[0036] [Item 10]

[0037] Use of the compound according to any one of [Item 1] to [Item 7] in the production of a polyester resin, a polycarbonate resin, a polyurethane resin or a polyester polyol resin.

[0038] [Item 11]

[0039] A method of using the compound described in any one of [Item 1] to [Item 7] as a monomer (as a raw material) of a polyester resin, a polycarbonate resin, a polyurethane resin or a polyester polyol resin.

[0040] [Item 12]

[0041] A polycarbonate resin comprising a structural unit represented by the general formula (2).

[0042]

[0043] [Where R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d).

[0044]

[0045] (In formulas (a) to (d), the wavy lines represent bonding sites. R 2 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms. )]

[0046] [Item 13]

[0047] A method for producing a compound represented by the general formula (1), comprising the step of reacting a compound represented by the general formula (3) with a compound represented by the general formula (4) in the presence of an acidic catalyst.

[0048]

[0049] [Where R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d).

[0050]

[0051] (In formulas (a) to (d), the wavy lines represent bonding sites. R 2 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms. )]

[0052] [Item 14]

[0053] The production method according to [item 13], wherein the compound represented by the general formula (3) is produced by reacting a compound represented by the general formula (5) with a compound represented by the general formula (6) in the presence of a base and then treating the reaction with an acid.

[0054]

[0055] [Where R 3represents an alkyl group. X is the same as above.]

[0056] Effects of the Invention

[0057] The cyclic diol compound of the present invention can be used as a resin raw material (monomer) or a resin modifier for polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, polyester polyol resins, and the like.

[0058] The resin (e.g., polycarbonate resin) obtained by using the monomer containing the cyclic diol compound of the present invention has a characteristic of having a large refractive index. Thus, by adjusting the content of the cyclic diol compound in the monomer, the refractive index of the obtained resin can be adjusted within a wide range. Therefore, the cyclic diol compound of the present invention is useful as a modifier for resins such as polycarbonate resins.

[0059] The resin (e.g., polycarbonate resin) has a negative birefringence characteristic. By copolymerizing the cyclic diol compound of the present invention with a dihydroxy compound having positive birefringence in an appropriate ratio, the birefringence of the resin can be infinitely close to zero. Therefore, the resin can be preferably used for optical purposes (optical lenses, optical films, optical sheets, etc.).

[0060] The cyclic diol compound of the present invention is produced by diacetalizing the carbonyl groups at the 1-position and the 3-position of the 1,3-cyclohexanedione ring. It is generally believed that diacetalization of 1,3-cyclohexanedione is extremely difficult due to steric hindrance, etc. However, the production method of the present invention uses a compound having an aromatic ring bonded to the 5-position of 1,3-cyclohexanedione as a raw material, so diacetalization is carried out efficiently, and the cyclic diol compound of the present invention can be produced in a good yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 IR spectrum of 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 1.

[0062] Figure 2 The 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 1 1 H-NMR spectrum.

[0063] Figure 3 This is the IR spectrum of 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal obtained in Example 2.

[0064] Figure 4 The 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal obtained in Example 2 1 H-NMR spectrum.

[0065] Figure 5This is the IR spectrum of 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 3.

[0066] Figure 6 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 3 1 H-NMR spectrum.

[0067] Figure 7 This is the IR spectrum of 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 4.

[0068] Figure 8 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 4 1 H-NMR spectrum.

[0069] Fig. 9 This is the IR spectrum of 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 5.

[0070] Fig.10 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 5 1 H-NMR spectrum.

[0071] Fig.11 This is the IR spectrum of 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 6.

[0072] Fig.12 The 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 6 1 H-NMR spectrum.

[0073] Fig.13 This is the IR spectrum of 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal obtained in Example 7.

[0074] Fig.14 The 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal obtained in Example 7 1 H-NMR spectrum.

[0075] Fig.15 This is the IR spectrum of 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 8.

[0076] Fig.165-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 8 1 H-NMR spectrum.

[0077] Fig.17 This is the IR spectrum of 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 9.

[0078] Fig.18 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 9 1 H-NMR spectrum.

[0079] Fig.19 This is the IR spectrum of 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 10.

[0080] Fig. 20 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 10 1 H-NMR spectrum.

[0081] Fig.21 This is the IR spectrum of 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 11.

[0082] Fig. 22 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 11 1 H-NMR spectrum.

[0083] Fig.23 This is the IR spectrum of 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 12.

[0084] Fig.24 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Example 12 1 H-NMR spectrum. DETAILED DESCRIPTION

[0085] The cyclic diol compound of the present invention is a compound represented by the following general formula (1).

[0086]

[0087] [Where R 1are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d).

[0088]

[0089] (In formulas (a) to (d), the wavy lines represent bonding sites. R 2 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms. )]

[0090] In the general formula (1), R 1 The "straight-chain or branched alkyl group having 1 to 4 carbon atoms" is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Among them, methyl, ethyl, isobutyl and tert-butyl are preferred, and methyl or ethyl is more preferred.

[0091] In the general formula (1), R 1 The "aryl group having 6 to 12 carbon atoms" is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, and naphthyl.

[0092] In the general formula (1), among the groups represented by the general formulas (a) to (d) represented by X, R 2 The "linear or branched alkyl group having 1 to 4 carbon atoms" is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like. 2 The "linear or branched alkoxy group having 1 to 7 carbon atoms" is not particularly limited, and examples thereof include methoxy, ethoxy, n-propoxy, and isopropoxy.

[0093] In the general formula (1), among the groups represented by the general formulas (a) to (d) represented by X, R 2 A hydrogen atom is preferred. Specifically, X includes a phenyl group (included in the general formula (a)), a biphenyl group (included in the general formula (b)), a 1-naphthyl group (included in the general formula (c)), and a 2-naphthyl group (included in the general formula (d)). Among them, a phenyl group is preferred.

[0094] In the general formula (1), R 1 Preferably, it is a methyl group or an ethyl group. X is preferably a group represented by the general formula (a), (c) or (d), more preferably a group represented by the general formula (a) or (d), and further preferably a group represented by the general formula (a). 2The same or different groups are each preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a methoxy group, an ethoxy group, etc., and more preferably a hydrogen atom.

[0095] In the general formula (1), X is a group represented by the general formula (a), and X is preferably a phenyl group or a group represented by the general formula (a1), (a2) or (a3) ​​shown below, and more preferably a phenyl group.

[0096]

[0097] [Where R 21 are the same or different and represent methyl, ethyl, isopropyl, sec-butyl, tert-butyl or methoxy.]

[0098] The compound represented by the general formula (1) is considered to exist in the following isomers such as isomer A, isomer B or isomer C. These isomers may be present alone or as a mixture of two or more.

[0099]

[0100] [Where R 1 and X are the same as above.]

[0101] When the cyclic diol compound of the present invention is a mixture of more than two isomers, the method described in the embodiment can be used to perform gas chromatography (GC) analysis and obtain the isomer ratio by the area percentage method. Each isomer usually has a characteristic peak by GC analysis. The ratio of the isomer content can be expressed by the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The ratio of the percentage of each isomer can be used as the isomer ratio.

[0102] The cyclic diol compound of the present invention is believed to exist in isomers such as the above-mentioned isomer A, isomer B or isomer C. Two isomer peaks are detected by GC analysis, and they are believed to be thermodynamically stable isomers A and B. The isomer ratio can be set in the range of isomer A:isomer B=80:20 to 50:50.

[0103] Specific examples of the compound represented by the general formula (1) include 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-ethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-fluoro-4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4,5-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-chloro-4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(pentamethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-biphenyl)-1,3-cyclohexanedione trimethylol Propane diacetal, 5-(3-bromo-4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-chlorobiphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,5-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-fluoro-3-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-biphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-bromo- 5-(5-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,5-di-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,3-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,6-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(5-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(5-bromo-2-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(1-naphthalene)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-naphthalene)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-ethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-isopropoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal 1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-propoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-chloro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-tert-butoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-dimethoxy-3-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal )-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-ethoxy-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-ethoxy-3-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-fluoro-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-pentyloxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal )-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,3,4-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4,6-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-chloro-3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-hexyloxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-bromo-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-heptyloxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-methoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-ethoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(6-methoxy-2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal Methylpropane diacetal; 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-ethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-fluoro-4-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal Methylolethane diacetal, 5-(2,4,5-trimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-chloro-4-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-butylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(pentamethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-biphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-bromo-4-methylphenyl)-1,3-cyclohexane 1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-chlorobiphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,5-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-fluoro-3-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-biphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-bromo-5-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,5-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal,5-(di-tert-butylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,3-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,6-dimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(5-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-fluoro-2-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(5-bromo-2-methylphenyl)-1,3-cyclohexanedione Hexanedione trimethylolethane diacetal, 5-(1-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-ethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-isopropoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-propoxyphenyl)-1,3 -cyclohexanedione trimethylolethane diacetal, 5-(2,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-chloro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-tert-butoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4-dimethoxy-3-methylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-ethoxy-4-methoxyphenyl) -1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-ethoxy-3-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-fluoro-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-pentyloxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,3,4-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2,4,6-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-chloro-3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-hexyloxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-bromo-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-heptyloxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal Ethane diacetal, 5-(2-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(3-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-methoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-methoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-ethoxy-1-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(6-methoxy-2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, etc.

[0104] Preferred compounds include 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal, 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(4-biphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(4-biphenyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(1-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5 -(1-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal, 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal, and as further preferred compounds are 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal and 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal.

[0105] The cyclic diol compound of the present invention can be produced, for example, as shown in the following <Reaction Formula 1>.

[0106] <Reaction 1>

[0107]

[0108] [Where R 1 and X are the same as above.]

[0109] As shown in the above <Reaction Formula 1>, the compound represented by the general formula (1) can be produced by reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) in the presence of an acidic catalyst (acetalization reaction). The reaction is usually carried out in a solvent (such as toluene, etc.). The reaction can be carried out while the solvent is heated to reflux and the generated water is removed azeotropically with the solvent. The acidic catalyst is not particularly limited as long as it has a catalytic effect, and a known acidic catalyst can be used. Examples thereof include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, aluminum silicates, heteropoly acids (such as phosphotungstic acid, phosphomolybdic acid, etc.); and various other Lewis acids. The amount of the compound represented by the general formula (4) used is usually about 0.5 to 3 mol, preferably about 0.8 to 2 mol, relative to 1 mol of the compound represented by the general formula (3).

[0110] Typically, as a method for producing the cyclic diol compound of the present invention, a 1,3-cyclohexanedione compound having a substituent X at the 5-position and a 1,3-cyclohexanedione compound having a substituent R at the 2-position are reacted with each other. 1 A method for producing a 2-hydroxymethyl-1,3-propanediol compound by acetalization reaction in a toluene solvent in the presence of an acidic catalyst.

[0111] In the present invention, since the compound represented by the general formula (3) has a substituent X at the 5-position of 1,3-cyclohexanedione, it is easier to undergo diacetalization with the compound represented by the general formula (4) than with 1,3-cyclohexanedione, and the target compound represented by the general formula (1) can be obtained in good yield.

[0112] The compound represented by the general formula (3) can be produced by reacting a compound represented by the general formula (5) with a compound represented by the general formula (6) in the presence of a base and then treating the reaction with an acid as shown in <Reaction Formula 2>.

[0113] <Reaction 2>

[0114]

[0115] [Where R 3 are the same or different, and each represents an alkyl group having 1 to 3 carbon atoms. X is the same as described above.]

[0116] As R 3 Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, and isopropyl.

[0117] This reaction can be carried out according to or based on a known method, for example, the method described in Chemistry-A European Journal (2017), 23(49), 11757-11760, Zhurnal Obshchei Khimii (1957), 27, 3087-92, etc.

[0118] The cyclic diol compound of the present invention can be used as a monomer of a polyester resin, a polycarbonate resin, an epoxy resin, a polyurethane resin, a polyacrylate resin, a polymethacrylate resin, a polyester polyol resin, or the like.

[0119] The present invention also provides a polycarbonate resin containing a structural unit represented by the following general formula (2): The polycarbonate resin can be produced by reacting (polymerizing) a monomer containing the cyclic diol compound of the present invention with a carbonyl precursor compound.

[0120]

[0121] [Where R 1 and X are the same as above.]

[0122] In the general formula (2), R 1 The specific examples and preferred examples of X are the same as those of R described in the above general formula (1). 1 The specific examples and preferred examples are the same as those of X.

[0123] The monomer containing the cyclic diol compound of the present invention may contain, in addition to the cyclic diol compound of the present invention, a dihydroxy compound generally used as a constituent unit of a polycarbonate resin, such as an aliphatic dihydroxy compound and an aromatic dihydroxy compound.

[0124] That is, the polycarbonate resin of the present invention may contain a structural unit derived from a common dihydroxy compound in addition to the structural unit represented by the general formula (2) derived from the cyclic diol compound of the present invention.

[0125] Examples of the aliphatic dihydroxy compound include various aliphatic dihydroxy compounds, and in particular, include 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 1,3-adamantanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-ol, isosorbide, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0126] Examples of the aromatic dihydroxy compound include various aromatic dihydroxy compounds, and in particular, include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, etc. In addition, hydroquinone, resorcinol, and catechol, etc., can also be mentioned.

[0127] The proportion of the cyclic diol compound of the present invention in the monomers used is not particularly limited, and is, for example, 1 to 80 mol%, preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total amount of the monomers. That is, in the polycarbonate resin of the present invention, the proportion of the structural unit represented by the general formula (2) derived from the cyclic diol compound of the present invention is not particularly limited, and is, for example, 1 to 80 mol%, preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total amount of the monomers.

[0128] Examples of the carbonyl precursor compound include phosgene, triphosgene, and diphenyl carbonate.

[0129] The polycarbonate resin containing the structural unit represented by the general formula (2) has a number average molecular weight (Mn) of about 10,000 to 100,000, a weight average molecular weight (Mw) of about 10,000 to 100,000, and a polydispersity index (Mw / Mn) of about 1 to 5. In addition, the glass transition temperature (Tg) is about 100 to 200.

[0130] The refractive index (n D ) is relatively large, usually 1.500 to 1.750, preferably 1.599 to 1.750. The refractive index is a value measured by the method described in the Examples.

[0131] The Abbe number (ν) of birefringence of the polycarbonate resin containing the structural unit represented by the general formula (2) is d ) is usually 20.0 to 55.0, preferably 25.0 to 33.0. The Abbe number is a value measured by the method described in the Examples.

[0132] The cyclic diol compound of the present invention (the compound represented by the general formula (1)) can be used as a resin modifier. Specifically, by using the cyclic diol compound of the present invention as a comonomer for copolymerization, the properties of the resin can be improved. For example, by adjusting the amount of the cyclic diol compound added to carry out copolymerization, the refractive index, birefringence and other properties of the resin can be adjusted. Examples of the target resin include polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, polyester polyol resins, etc. Typical of these are polyester resins and polycarbonate resins.

[0133] Generally, when birefringence observed in polymerized optical materials is classified into orientation birefringence, stress birefringence and morphological birefringence. Among them, morphological birefringence is the birefringence observed when fine fibrous substances in the resin are arranged, so it is usually negligible as the optical properties of optical materials. Orientation birefringence is birefringence based on molecular orientation, and stress birefringence is caused by residual stress during molding.

[0134] For polymers used as optical materials, if the birefringence is large, the optical strain will be large, so when used for lens applications, for example, problems such as burrs and blurring will occur. Therefore, in order to image more clearly, it is necessary to reduce the birefringence.

[0135] There are various polymers commonly used for optical materials, including polyester resins, polycarbonate resins, etc., and polycarbonate resins are particularly excellent in transparency, impact resistance, heat resistance, dimensional stability, etc. However, bisphenol A type polycarbonate resins have large birefringence, and in order to use them for optical materials, the birefringence needs to be reduced.

[0136] The resin (particularly polycarbonate resin) obtained by copolymerization of the cyclic diol compound of the present invention has negative birefringence, therefore, by making a resin copolymerized with the constituent units of the cyclic diol compound of the present invention and other dihydroxy compounds showing positive birefringence, birefringence can be made infinitely close to zero. The resin can be preferably used for purposes requiring birefringence to be infinitely close to zero, especially optical materials such as optical lenses, optical films, and optical sheets. As applicable optical materials, there is no particular limitation, and for example, lenses of cameras of smartphones, lenses of vehicle-mounted cameras, goggles lenses for VR (virtual reality) or MR (mixed reality), lenses for anti-crime cameras, etc. can be cited.

[0137] In addition, the resin (particularly polycarbonate resin) copolymerized with the cyclic diol compound of the present invention has a characteristic of having a large refractive index. Therefore, by adjusting the content of the cyclic diol compound of the present invention, the refractive index of the resin can be adjusted in a wide range according to the design of various lenses.

[0138] In this specification, the expression "comprising" or "including" includes "consisting of" and "consisting of".

[0139] Example

[0140] The present invention is described in detail below with reference to the following examples, but the present invention is not limited to these examples. It should be noted that in the present examples, various determinations of cyclic diol compounds were performed according to the following methods. In addition, chemical reagents were used for compounds not specifically stated.

[0141] <Compounds used>

[0142] 5-Phenyl-1,3-cyclohexanedione: Made by Combi-Blocks Co., Ltd.

[0143] · Phosphotungstic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0144] · Trimethylolethane and trimethylolpropane: manufactured by Tokyo Chemical Industry Co., Ltd.

[0145] ·Bisphenoxyethanol fluorene: manufactured by Tokyo Chemical Industry Co., Ltd.

[0146] ·Diphenyl carbonate: manufactured by Tokyo Chemical Industry Co., Ltd.

[0147] ·4-tert-Butylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0148] ·2,4,6-Trimethylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0149] ·2,4-Dimethylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0150] ·2-Naphthaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0151] ·4-Methylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0152] ·3,4-Dimethylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0153] ·4-Methoxybenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0154] ·4-Isopropylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0155] ·4-isobutylbenzaldehyde: manufactured by Tokyo Chemical Industry Co., Ltd.

[0156] ·Toluene: Manufactured by Nakalaku Co., Ltd.

[0157] ·Acetone: Manufactured by NARARUSH CO., LTD.

[0158] ·Diethyl malonate: manufactured by Tokyo Chemical Industry Co., Ltd.

[0159] <Analysis by gas chromatography (GC)>

[0160] Gas chromatography (GC) analysis was performed under the following conditions and method, and the purity of the cyclic diol compound was determined by the area percentage method.

[0161] [Sample preparation]

[0162] To 0.1 g of the cyclic diol compound was added 10 ml of pyridine, and the mixture was shaken and mixed at room temperature to prepare a sample for analysis.

[0163] [Measurement conditions]

[0164] Equipment: GC-2020 manufactured by Shimadzu Corporation

[0165] Column: DB-1 30m×0.25mm×0.25μm manufactured by Agilent Technologies

[0166] Column temperature: 80°C (retention time 5 minutes) - heating rate 15°C / min - 320°C (retention time 5 minutes)

[0167] Injection temperature / detector temperature: 300℃ / 325℃ Split ratio: 30 Column flow rate: 1.17ml / min Purge flow rate: 3.0ml / min

[0168] Detector: FID

[0169] Carrier gas: Helium

[0170] Gas linear velocity: 30cm / s

[0171] Injection volume: 1 μl

[0172] <Melting point>

[0173] The melting point of the cyclic diol compound was measured using a differential calorimeter DSC6220 manufactured by Essence International Nanotechnological Co., Ltd. 6.8 mg of the sample was placed in an aluminum pan manufactured by the company and sealed, and the temperature was raised from 30°C to 200°C at a heating rate of 10°C / min under a nitrogen gas flow of 50 ml / min, and the endothermic peak was observed. The temperature shown at the peak top was taken as the melting point.

[0174] <Infrared absorption spectrum (IR spectrum)>

[0175] The IR spectrum of the cyclic diol compound was measured by the ATR method (attenuated total reflectance method) using an infrared spectrometer (Spectrum 400 manufactured by Parakin Elmer Japan Co., Ltd.).

[0176] <Proton NMR spectroscopy( 1 H-NMR)>

[0177] About cyclic diol compounds 1 H-NMR was performed by dissolving the sample in a deuterated solvent (deuterated chloroform, deuterated methanol, deuterated dimethyl sulfoxide, etc.) and using a nuclear magnetic resonance apparatus (DRX-500 manufactured by Bruker). 1 The results were obtained by H-NMR (500 MHz) measurement.

[0178] It should be noted that 1 Water peaks may be observed in the solvent used for H-NMR measurement. The peak derived from water contained in deuterated chloroform is present at around 1.56 ppm, the peak derived from water contained in deuterated methanol is present at around 4.87 ppm, and the peak derived from water contained in deuterated dimethyl sulfoxide is present at around 3.33 ppm.

[0179] <Glass transition temperature>

[0180] The glass transition temperature of the obtained polycarbonate resin was measured using a differential calorimeter DSC6220 manufactured by Essence Iii Nanotech Co., Ltd. 6.7 mg of the sample was placed in an aluminum pan manufactured by the company and sealed, and the temperature was raised from 30°C to 220°C at a heating rate of 10°C / min under a nitrogen gas flow of 50 ml / min, cooled from 220°C to 30°C at a cooling rate of 10°C / min, and then raised from 30°C to 220°C at a heating rate of 10°C / min, and the inflection point in the 2nd RUN was taken as the glass transition temperature.

[0181] <Number average molecular weight, weight average molecular weight and polydispersity index>

[0182] About 30 mg of polycarbonate resin was dissolved in 8 ml of tetrahydrofuran to prepare a sample solution for molecular weight measurement. Regarding the number average molecular weight Mn and the weight average molecular weight Mw, the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (Mw / Mn) calculated based on polystyrene were determined using gel permeation chromatography (GPC) under the following measurement conditions.

[0183] (Measurement conditions)

[0184] Device: Pump (LC-20AD model manufactured by Shimadzu Corporation)

[0185] Automatic sample injector (SIL-20A HT model manufactured by Shimadzu Corporation)

[0186] Detector RI (RID-10A manufactured by Shimadzu Corporation)

[0187] Column thermostat (model CTO-20A manufactured by Shimadzu Corporation)

[0188] Column: Shodex LF-802, 2 pieces (manufactured by Showa Denko K.K.)

[0189] Eluent: Tetrahydrofuran (THF) manufactured by Nacalai Tesque Co., Ltd. containing about 0.025% BHT

[0190] Column temperature: 40°C

[0191] Flow rate: 1.0mL / min

[0192] Injection volume: 100 μl

[0193] Analysis method: PS converted molecular weight

[0194] Use standard polymer: Shodex STANDARD SM-105

[0195] <Refractive Index>

[0196] A rectangular test piece with a length of 4.0 mm and a width of 0.8 mm was cut out from a film with a thickness of 0.1 mm produced in the reference example described later as a measurement sample. The refractive index n was measured using an interference filter with a wavelength of 589 nm (D-ray) using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. according to the method of JIS-K-7142. D In the measurement, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as an intermediate liquid.

[0197] <Birefringence>

[0198] For the sample, a heated uniaxial stretching was performed using the tensile fixture provided in the solid viscoelasticity measuring device (UBM, S1000-DVE3). After the stretching stopped, the thermostatic bath was opened and cooled with a blower. For the stretched film, the LA-100USW manufactured by HAYASHI-REPIC Co., Ltd. was used as the light source device, and the phase difference measuring device KOBRA-WPR manufactured by Prince Instruments Co., Ltd. was used to measure the phase difference at each wavelength of 449.9nm, 498.0nm, 548.0nm, 588.8nm, 628.8nm, and 751.0nm. The birefringence Δn was calculated by the following formula from the phase difference of the obtained wavelength of 548.0nm and the wavelength of 588.8nm and the film thickness of the stretched film. It should be noted that when the slow axis is consistent with the stretching direction, Δn is expressed as a positive value, and when the slow axis is consistent with the vertical direction, Δn is expressed as a negative value.

[0199] Birefringence Δn = (phase difference at measurement wavelength 548.0 nm [nm]) / (film thickness [mm] × 10 6 )

[0200] Birefringence Δn = (phase difference at measurement wavelength 588.8 nm [nm]) / (film thickness [mm] × 10 6 )

[0201] <Abbe number>

[0202] A rectangular test piece of 4.0 mm in length and 0.8 mm in width was cut from a film of 0.1 mm in thickness prepared in the reference example described below as a measurement sample. The refractive index n of each wavelength was measured using interference filters of wavelengths 656 nm (C ray), 589 nm (D ray), and 486 nm (F ray) using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. according to the method of JIS-K-7142. C 、n D 、n F , the Abbe number ν is calculated from these measured values ​​and the following formula d .

[0203] ν d =(1-n D ) / (n C -n F )

[0204] In the measurement, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as an intermediate liquid.

[0205] <Total light transmittance>

[0206] The 0.1 mm thick film prepared by the above method was used as a measurement sample, and the total light transmittance was measured using Haze Meter NDH7000SPII manufactured by Nippon Denshoku Co., Ltd. according to the method of JIS-K-7136. The measurement was performed on three films, and the average of the measured values ​​obtained in the measurement was taken as the measured value.

[0207] [Example 1]

[0208] 12.5 g (66.4 mmol) of 5-phenyl-1,3-cyclohexanedione, 625 mg of phosphotungstic acid, 21.3 g (159 mmol) of trimethylolpropane, and 125 ml of toluene were added to a 300 ml eggplant flask equipped with a condenser and a Dean-Stark, and then placed in a stirrer. The mixture was heated while being stirred with a magnetic stirrer, and the acetal reaction was carried out for 2 hours while the generated water gradually flowed out with a Dean-Stark removal with the target of the theoretical generated water amount (132 mmol, 2.3 g) under toluene reflux.

[0209] The reaction mixture was returned to room temperature, neutralized with 125 ml of saturated sodium bicarbonate aqueous solution, and then 125 ml of toluene was added to separate the aqueous layer and the organic layer. The separated organic layer was washed with 125 ml of warm water at 40°C. The organic layer was set to 40°C and 50 mmHg, and the solvent was removed by an evaporator. The remaining organic layer 125 g was stirred at room temperature and the crystals were taken out. Toluene was used as an eluent to filter out the precipitated crystals. 16.0 g of the wet crystals were dried under 5 mmHg and 100°C to obtain 11.8 g (28 mmol) of 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 1") with a purity of 99.6% (GC area percentage). The melting point of the crystals is 135°C.

[0210] For the obtained compound 1, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Figure 1 and Figure 2 The following characteristic peaks shown in the figure confirmed that the product was 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal.

[0211] IR(cm -1 ): 3365, 2965, 2948, 2869, 1474, 1463, 1358, 1263, 1253, 1191, 1162, 1087, 1061, 1031, 1000, 969, 820, 756, 699

[0212] 1 H-NMR (500MHz, ppm, CDCl3): 0.80 (t, 3H), 0.87 (t, 3H), 1.24 (m, 2H), 1.33 (m, 2H), 1.39 (t, 1H), 1.49 (d, 1H), 1.67 (t, 1H), 1.96 (d, 2H), 2.18 (d, 1H), 2.76 (d, 1H), 2.94 (m, 2H), 3.70 (m, 10H), 3.82 (m, 2H), 7.20 (m, 3H), 7.31 (m, 2H)

[0213] (It should be noted that the peak near 7.26 ppm is a peak derived from chloroform contained in the deuterated chloroform solvent.

[0214] [Example 2]

[0215] The same operation as in Example 1 was carried out except that trimethylolpropane was replaced with 19.1 g (159 mmol) of trimethylolethane, to obtain 11.0 g (28 mmol) of 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal (hereinafter referred to as "Compound 2") having a purity of 95.1% (GC area percentage). The melting point of the crystals was 135°C.

[0216] For the obtained compound 2, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Figure 3 and Figure 4 The following characteristic peaks shown in the figure confirmed that it was 5-phenyl-1,3-cyclohexanedione trimethylolethane diacetal.

[0217] IR(cm -1 ): 3467, 3415, 2944, 2928, 2876, 1474, 1359, 1245, 1206, 1199, 1159, 1089, 1050, 1027, 969, 819, 764, 699

[0218] 1 H-NMR (500MHz, ppm, CDCl3): 0.70 (s, 6H), 1.46 (t, 2H), 1.72 (d, 1H), 2.20 (s, 2H), 2.48 (d, 1H), 2.81 (m, 3H), 3.72 (m, 12H), 7.26 (m, 3H), 7.36 (m, 2H)

[0219] (It should be noted that the peak near 7.26 ppm is a peak derived from chloroform contained in the deuterated chloroform solvent.

[0220] [Example 3]

[0221] 42.8 g (264 mmol) of 4-tert-butylbenzaldehyde and 396 ml of acetone were added to a 1 L beaker, and 264 g of a 10 wt% aqueous sodium hydroxide solution was added dropwise at a temperature below 30° C. The mixture was then stirred at room temperature for 2.5 hours, neutralized with 44 g of acetic acid, and the acetone was distilled off.

[0222] 264 ml of ethyl acetate was added and the organic layer was separated. The obtained organic layer was washed with a saturated sodium bicarbonate aqueous solution and a saturated sodium chloride aqueous solution in sequence and concentrated under reduced pressure to obtain 65.1 g of a pale yellow liquid with a purity of 90.7% (GC area percentage). The obtained crude reaction product was subjected to reduced pressure single distillation at 141-145° C. and 0.1-0.2 kPa to obtain 35.4 g of a pale yellow liquid with a purity of 98.8% (GC area percentage).

[0223] In a 500 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a condenser, 30 ml of ethanol, 17.4 g (110 mmol) of diethyl malonate and 37.4 g (110 mmol) of a 20 wt% sodium ethanol ethanol solution were added and stirred at room temperature for 30 minutes. The temperature was then raised to 70°C, and a solution prepared by dissolving 20.2 g (100 mmol) of 4-tert-butylbenzylideneacetone in 30 ml of ethanol was added dropwise over 25 minutes at the same temperature. 80 ml of ethanol was then added, the temperature was raised, and the mixture was stirred under reflux for 2 hours.

[0224] Then, hydrolysis was carried out under reflux for 2 hours with a 10 wt% sodium hydroxide aqueous solution, and then 150 ml of ethanol was distilled off under reduced pressure from normal pressure. Then, after cooling to room temperature, 80 g of a 20 wt% hydrogen chloride aqueous solution was added, and decarbonation reaction was carried out under reflux for 4 hours. The precipitated crystals were rinsed 4 times with 50 ml of water and dried under reduced pressure to obtain 25.6 g of crude crystals with a purity of 91.3% (GC area percentage). Then, 200 ml of ethyl acetate was added, stirred at 70°C for 1 hour, and rinsed with 50 ml of ethyl acetate to filter out the precipitated crystals. After drying under reduced pressure at 100°C for 2 hours, 19.7 g of solids of different shades of color with a purity of 98.9% (GC area percentage) were obtained.

[0225] 5-(4-tert-butylphenyl)-1,3-cyclohexanedione 12.4g (50mmol), trimethylolpropane 16.8g (125mmol), phosphotungstic acid 625mmg, toluene 120ml were added to a 500ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a condenser with a water separator, and heated and stirred at reflux temperature for 2.5 hours. After the reaction was completed, it was cooled to room temperature, saturated sodium bicarbonate aqueous solution 50ml was added and stirred for 0.5 hours. Then ethyl acetate 50ml was added, and the obtained organic layer was washed with warm water and concentrated under reduced pressure to obtain 23.5g of diacetal crude product. During the purification of the crude product, 90 g of toluene was used for recrystallization, filtration, filter cake washing (40 ml of cold toluene), and reduced pressure drying at 100°C for 2 hours to obtain 14.8 g of 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 3") with a purity of 98.5% (GC area percentage).

[0226] For the obtained compound 3, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Figure 5 and Figure 6 From this, it was confirmed to be 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0227] IR(cm -1): 3390, 2961, 2868, 1462, 1359, 1252, 1194, 1163, 1089, 1030, 999, 971, 833, 730

[0228] 1 H-NMR (500MHz, ppm, CDCl3): Reference Figure 6 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0229] [Example 4]

[0230] 50 g (337 mmol) of 2,4,6-trimethylbenzaldehyde was added to a 1 L beaker. The same operation as in Example 3 was carried out except that the mixture was diluted with 15.6 g of 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 4") having a purity of 96.7% (GC area percentage).

[0231] For the obtained compound 4, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Figure 7 and Figure 8 From this, it was confirmed to be 5-(2,4,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0232] IR(cm -1 ): 3502, 2961, 2866, 1459, 1346, 1210, 1169, 1091, 1050, 1032, 976, 802

[0233] 1 H-NMR (500MHz, ppm, CDCl3): Reference Figure 8 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0234] [Example 5]

[0235] The same operation as in Example 3 was carried out except that 50 g (373 mmol) of 2,4-dimethylbenzaldehyde was added to a 1 L beaker to obtain 5.3 g of 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 5") having a purity of 98.8% (GC area percentage).

[0236] For the obtained compound 5, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig. 9 and Fig.10From this, it was confirmed to be 5-(2,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0237] IR(cm -1 ): 3366, 2955, 2863, 1361, 1089, 1033, 976, 808

[0238] 1 H-NMR (500MHz, ppm, CDCl3): Reference Fig.10 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0239] [Example 6]

[0240] The same operation as in Example 3 was carried out except that 25 g (160 mmol) of 2-naphthaldehyde was added to a 1 L beaker to obtain 31.2 g of 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 6") having a purity of 94.6% (GC area percentage).

[0241] For the obtained compound 6, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.11 and Fig.12 From this, it was confirmed to be 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0242] IR(cm -1 ): 3350, 2964, 2869, 1358, 1181, 1160, 1088, 1062, 1033, 972, 745

[0243] 1 H-NMR (500MHz, ppm, CD3OD): Reference Fig.12 (It should be noted that the peak near 3.31 ppm is derived from methanol contained in the solvent deuterated methanol.

[0244] [Example 7]

[0245] The same operation as in Example 3 was carried out except that 25 g (160 mmol) of 2-naphthaldehyde was added to a 1 L beaker to obtain 5.8 g of 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal (hereinafter referred to as "Compound 7") having a purity of 93.9% (GC area percentage).

[0246] For the obtained compound 7, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.13 and Fig.14 From this, it was confirmed to be 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolethane diacetal.

[0247] IR(cm -1 ): 3389, 2952, 2872, 1448, 1348, 1198, 1085, 1041, 980, 746

[0248] 1 H-NMR (500MHz, ppm, CD3OD): Reference Fig.14 (It should be noted that the peak near 3.31 ppm is derived from methanol contained in the solvent deuterated methanol.

[0249] [Example 8]

[0250] The same operation as in Example 3 was carried out except that 48 g (400 mmol) of 4-methylbenzaldehyde was added to a 1 L beaker to obtain 12.6 g of 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 8") having a purity of 95.8% (GC area percentage).

[0251] For the obtained compound 8, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.15 and Fig.16 From this, it was confirmed to be 5-(4-methylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0252] IR(cm -1 ): 3399, 2960, 2866, 1356, 1159, 1088, 1031, 971, 820, 783

[0253] 1 H-NMR (500MHz, ppm, CDCl3): Reference Fig.16 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0254] [Example 9]

[0255] The same operation as in Example 3 was carried out except that 26.8 g (200 mmol) of 3,4-dimethylbenzaldehyde was added to a 1 L beaker to obtain 14.5 g of 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 9") with a concentration of 98.3% (GC area percentage).

[0256] For the obtained compound 9, the IR spectrum and 1H-NMR spectrum. The obtained results are shown in Fig.17 and Fig.18 From this, it was confirmed to be 5-(3,4-dimethylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0257] IR(cm -1 ): 3373, 2963, 2869, 1356, 1172, 1088, 1055, 1031, 972

[0258] 1 H-NMR (500MHz, ppm, CDCl3): Reference Fig.18 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0259] [Example 10]

[0260] The same operation as in Example 3 was carried out except that 20.4 g (150 mmol) of 4-methoxybenzaldehyde was added to a 1 L beaker to obtain 2.9 g of 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 10") having a purity of 97.3% (GC area percentage).

[0261] For the obtained compound 10, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.19 and Fig. 20 From this, it was confirmed to be 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0262] IR(cm -1 ): 3404, 2952, 2878, 1514, 1355, 1238, 1157, 1088, 1031, 971, 830

[0263] 1 H-NMR (500MHz, ppm, DMSO-d6): Reference Fig. 20 (It should be noted that the peak near 2.50 ppm is derived from dimethyl sulfoxide contained in the solvent deuterated dimethyl sulfoxide.

[0264] [Example 11]

[0265] The same operation as in Example 3 was carried out except that 44.4 g (300 mmol) of 4-isopropylbenzaldehyde was added to a 1 L beaker to obtain 44.4 g of 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 11") having a purity of 99.3% (GC area percentage).

[0266] For the obtained compound 11, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.21 and Fig. 22 From this, it was confirmed to be 5-(4-isopropylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0267] IR(cm -1 ): 3392, 2959, 2866, 1357, 1161, 1088, 1054, 1029, 970

[0268] 1 H-NMR (500MHz, ppm, CDCl3): Reference Fig. 22 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0269] [Example 12]

[0270] The same operation as in Example 3 was carried out except that 50 g (308 mmol) of 4-isobutylbenzaldehyde was added to a 1 L beaker to obtain 12.2 g of 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 12") having a purity of 98.1% (GC area percentage).

[0271] For the obtained compound 12, the IR spectrum and 1 H-NMR spectrum. The obtained results are shown in Fig.23 and Fig.24 From this, it was confirmed to be 5-(4-isobutylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal.

[0272] IR(cm -1 ): 3398, 2955, 2867, 1358, 1159, 1088, 1054, 1029, 970, 729

[0273] 1 H-NMR (500MHz, ppm, CDCl3): Reference Fig.24 (It should be noted that the peak near 7.26 ppm is derived from chloroform contained in the deuterated chloroform solvent.

[0274] <Production of polymers>

[0275] [Production Example 1]

[0276] 11.8 g (0.03 mol) of compound 1 obtained in Example 1, 48.5 g (0.11 mol) of bisphenoxyethanol fluorene, 30.5 g (0.14 mol) of diphenyl carbonate, and 2.5×10 -2 mol / L sodium bicarbonate aqueous solution 54.90 μL (13.9×10 - 7 mol) was added into a 300 mL four-necked flask equipped with a stirrer and a distillation device, stirred and heated to 200° C. under a nitrogen atmosphere.

[0277] After the matrix is ​​dissolved, the temperature is gradually raised to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg. The pressure is gradually reduced to vacuum over 40 minutes, and maintained for 20 minutes, and then 45 g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") is taken out. It should be noted that during the reaction, the by-product phenol is distilled off. The taken-out polycarbonate resin 1 is crushed and the glass transition temperature is measured, and the result is 148°C. The number average molecular weight Mn is 31,600, the weight average molecular weight Mw is 63,800, and the polydispersity index Mw / Mn is 2.0. The results obtained are shown in Table 1.

[0278] [Production Example 2]

[0279] In the same manner as in Preparation Example 1, 11.4 g (0.03 mol) of the compound 2 obtained in Example 2, 48.5 g (0.11 mol) of bisphenoxyethanol fluorene, 30.5 g (0.14 mol) of diphenyl carbonate, and 2.5×10 -2 mol / L sodium bicarbonate aqueous solution 58.16 μL (14.5×10 -7 40 g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") produced by 0.1% mol was taken out. The taken out polycarbonate resin 2 was crushed and the glass transition temperature was measured. The result was 152°C. The number average molecular weight Mn was 16900, the weight average molecular weight Mw was 32800, and the polydispersity index Mw / Mn was 1.9. The obtained results are shown in Table 1.

[0280] [Production Example 3]

[0281] In the same manner as in Preparation Example 1, 6.48 g (0.01 mol) of the compound 3 obtained in Example 3, 23.85 g (0.05 mol) of bisphenoxyethanol fluorene, 15.0 g (0.07 mol) of diphenyl carbonate, and 2.5×10 -2 mol / L sodium bicarbonate aqueous solution 26.9 μL (6.7×10 -725 g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") produced by 0.1% mol was taken out. The taken out polycarbonate resin 3 was crushed and the glass transition temperature was measured. The result was 146°C. The number average molecular weight Mn was 9507, the weight average molecular weight Mw was 32100, and the polydispersity index Mw / Mn was 3.4. The obtained results are shown in Table 1.

[0282] <Polycarbonate resin properties>

[0283] [Reference Example 1]

[0284] For the polycarbonate resin 1 obtained in Manufacturing Example 1, 0.8 g of the resin was heated at 240°C for 1 minute under a pressure of 1 MPa using a compression molding machine manufactured by Shinto Metal Industries Co., Ltd., and then heated at a pressure of 20 MPa for 30 seconds, and then heated at a pressure of 10 MPa for 1 minute and 30 seconds. After that, a cooling operation was performed for 3 minutes to obtain a polycarbonate film. The physical properties of the obtained polycarbonate film were measured. The refractive index was 1.614. The birefringence at a wavelength of 548.0 nm was -0.36×10 -3 The birefringence at a wavelength of 588.8 nm is -0.31×10 -3 The Abbe number was 25.6. The total light transmittance was 89%. The obtained results are shown in Table 1.

[0285] [Reference Example 2]

[0286] The polycarbonate film was obtained in the same manner as in Reference Example 1 except that 0.8 g of the polycarbonate resin 2 obtained in Preparation Example 2 was used as the resin amount. The physical properties of the obtained polycarbonate film were measured. The refractive index was 1.619. The birefringence at a wavelength of 548.0 nm was -0.34×10 -3 The birefringence at a wavelength of 588.8 nm is -0.34×10 -3 The Abbe number was 26.9. The total light transmittance was 89%. The obtained results are shown in Table 1.

[0287] [Table 1]

[0288]

[0289] From the above results, it was confirmed that the polycarbonate resin obtained by copolymerizing the cyclic diol compound of the present invention has a large refractive index and negative birefringence.

[0290] [Reference Example 3]

[0291] In the same manner as in Preparation Example 1 and Reference Example 1, 5.8 g (0.01 mol) of Compound 1, 54.5 g (0.12 mol) of bisphenoxyethanolfluorene, 30.5 g (0.14 mol) of diphenyl carbonate, and 2.5×10 -2mol / L sodium bicarbonate aqueous solution 56.0 μL (14.2×10 -7 The polycarbonate film was prepared by mixing 100 mol of polycarbonate. The physical properties of the obtained polycarbonate film were measured. The refractive index was 1.625.

[0292] [Reference Example 4]

[0293] In the same manner as in Preparation Example 1 and Reference Example 1, 46.5 g (0.11 mol) of Compound 1, 12.1 g (0.02 mol) of bisphenoxyethanolfluorene, 30.5 g (0.14 mol) of diphenyl carbonate, and 2.5×10 -2 mol / L sodium bicarbonate aqueous solution 56.0 μL (14.2×10 -7 The polycarbonate film was prepared by mixing 100 mol of polycarbonate. The physical properties of the obtained polycarbonate film were measured. The refractive index was 1.562.

[0294] From the above results, it was confirmed that the refractive index of the polycarbonate resin obtained can be adjusted by performing copolymerization by changing the content of the cyclic diol compound of the present invention.

[0295] Industrial Applicability

[0296] The cyclic diol compound of the present invention can be used as a monomer or resin modifier for polyester resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, polyester polyol resins, etc. In particular, polycarbonate resins containing constituent units derived from cyclic diol compounds are suitable as optical materials because they have a large refractive index and negative birefringence.

Claims

1. A compound represented by the general formula (1), In the formula, R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms; X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d), In formulas (a) to (d), the wavy lines represent the bonding sites, and R 2 The same or different groups each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

2. The compound according to claim 1, wherein In the general formula (1), R 1 are the same or different and are each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.

3. The compound according to claim 2, wherein In the general formula (1), R 1 The same or different, each is methyl or ethyl.

4. The compound according to any one of claims 1 to 3, wherein In the general formula (1), among the groups represented by the general formulas (a) to (d) represented by X, R 2 The same or different groups are each a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

5. The compound according to claim 4, wherein In the general formula (1), X is a phenyl group, a biphenyl group, a 1-naphthyl group or a 2-naphthyl group.

6. The compound according to claim 5, wherein In the general formula (1), X is a phenyl group. 7 . A monomer for a polyester resin, a polycarbonate resin, a polyurethane resin or a polyester polyol resin, comprising the compound according to claim 1 . 8 . A resin modifier for polyester resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethacrylate resin or polyester polyol resin, comprising the compound according to claim 1 . 9 . A method of using the compound according to claim 1 as a monomer of a polyester resin, a polycarbonate resin, a polyurethane resin or a polyester polyol resin.

10. A method for producing a compound represented by general formula (1), comprising the step of reacting a compound represented by general formula (3) with a compound represented by general formula (4) in the presence of an acidic catalyst, In the formula, R 1 are the same or different and each represents a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms; X represents a group represented by the following general formula (a), general formula (b), general formula (c) or general formula (d), In formulas (a) to (d), the wavy lines represent the bonding sites, and R 2 The same or different groups each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

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