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

Abstract

The present invention provides a modifier for resins such as polyester resins, polyester carbonate resins, and polycarbonate resins. The present invention further provides a cyclic diol compound useful as a resin modifier and a method for producing the compound. The present invention relates to a resin modifier comprising a compound represented by general formula (1). [In the formula, the R1 moieties may be the same or different and each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a C1-C4 linear or branched alkyl group, and ring A represents a benzene ring optionally substituted by one to four groups selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, C1-C6 linear or branched alkoxy groups, and C1-C6 linear or branched alkyl groups.]

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 technology]

[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, and 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A). In addition to these, various cyclic diol compounds have been reported depending on the application of the resin to be produced.

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

[0004] However, the properties of resins such as polyester resins and polycarbonate resins vary widely depending on the various application fields in which the resins are used, and a search is underway for a cyclic diol compound that can satisfy the resin properties required in those fields. In particular, when a resin is used for optical purposes, a cyclic diol compound that can improve the optical properties of the resin is required. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2012-214803 A [Patent Document 2] JP 2013-001867 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a modifier for resins such as polyester resins, polyester carbonate resins, polycarbonate resins, etc. Another object of the present invention is to provide a cyclic diol compound useful as a resin modifier, and a method for producing the same. [Means for solving the problem]

[0007] The present inventors have conducted intensive research to solve the above problems, and have found that a cyclic diol compound having a diacetal structure represented by formula (1) can be incorporated as a structural unit (repeating unit) in a resin to modify the physical properties of the resin and produce a resin having new physical properties. Specifically, the inventors have found that the cyclic diol compound is useful as a raw material (monomer) or modifier for resins such as polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic ester resins, polymethacrylic ester resins, and polyester polyol resins. Based on this knowledge, the inventors have conducted further research and have completed the present invention.

[0008] That is, the present invention provides a resin modifier comprising a cyclic diol compound, a cyclic diol compound, and a method for producing the compound, as described below.

[0009] [Section 1] A resin modifier comprising a compound represented by general formula (1) (hereinafter also referred to as a "cyclic diol compound"). [ka] [In the formula, R 1are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms. Ring A represents a benzene ring optionally substituted with 1 to 4 groups selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.] [Section 2] The resin modifier is a modifier for one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins and polyester polyol resins. The resin modifier according to [Item 1]. [Section 3] In the general formula (1), R 1 are the same or different and are each a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group. [Item 1] or [Item 2] The resin modifier according to the present invention. [Section 4] In the general formula (1), R 1 are the same or different and are each a methyl group or an ethyl group. [Section 5] The resin modifier according to any one of [Item 1] to [Item 4], wherein in general formula (1), ring A is a benzene ring optionally substituted with 1 to 4 groups selected from the group consisting of linear or branched alkoxy groups having 1 to 6 carbon atoms and linear or branched alkyl groups having 1 to 6 carbon atoms. [Section 6] In the general formula (1), R 1 is a methyl group or an ethyl group, and ring A is a benzene ring optionally substituted with 1 to 4 groups selected from the group consisting of methyl groups and ethyl groups. [Section 7] The resin modifier according to any one of [Item 1] to [Item 6], wherein in general formula (1), ring A is a benzene ring. [Section 8] The resin modifier according to [Item 1] or [Item 2], wherein the compound represented by general formula (1) is a compound represented by general formula (1a). [ka] [In the formula, R 2 R are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. 1 Same as above.] [Section 9] The resin modifier according to [Item 1] or [Item 2], wherein the compound represented by general formula (1) is a compound represented by general formula (1b). [ka] [In the formula, R 1 and R 2 Same as above.] [Section 10] The resin modifier according to [Item 1] or [Item 2], wherein the compound represented by general formula (1) is a compound represented by general formula (1c): [ka] [In the formula, R 1 and R 2 Same as above.] [Section 11] A resin raw material monomer consisting of a compound represented by general formula (1). [Section 12] A compound represented by general formula (1a): [ka] [In the formula, R 1 and R 2 Same as above.] [Section 13] A compound represented by general formula (1c): [ka] [In the formula, R 1 and R 2 Same as above.] [Section 14] R 1 are the same or different and each is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group. [Section 15] R 1 and are the same or different and each is a methyl group or an ethyl group. [Section 16] R 2 and are the same or different and each is a hydrogen atom, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. [Section 17] R 1 are the same or different and each is a methyl group or an ethyl group, R 2 and are the same or different and each is a hydrogen atom, a methyl group, or an ethyl group. [Section 18] R 2 are all hydrogen atoms. [Section 19] A method for producing a compound represented by general formula (1), comprising a step of reacting a compound represented by general formula (3) with a compound represented by general formula (4) (acetalization reaction). [ka] [In the formula, R 1 and ring A is the same as above.] [Section 20] A method for producing a compound represented by general formula (1a), comprising a step of reacting a compound represented by general formula (3a) with a compound represented by general formula (4) (acetalization reaction). [ka] [In the formula, R 1 and R 2 Same as above.] [Section 21] A method for producing a compound represented by general formula (1c), comprising a step of reacting a compound represented by general formula (3c) with a compound represented by general formula (4) (acetalization reaction). [ka] [In the formula, R 1 and R 2 Same as above.] [Section 22] A polycarbonate resin containing a structural unit (repeating unit) represented by general formula (2). [ka] [In the formula, R 1 and ring A is the same as above.] [Section 23] The polycarbonate resin according to

[22] , containing a constitutional unit (repeating unit) represented by general formula (2a). [ka] [In the formula, R 1 and R 2 Same as above.] [Section 24] The polycarbonate resin according to

[22] , containing a constitutional unit (repeating unit) represented by general formula (2c): [ka] [In the formula, R 1 and R 2 Same as above.] [Section 25] The polycarbonate resin according to

[22] , containing a constitutional unit (repeating unit) represented by general formula (2b): [ka] [In the formula, R 1 and R 2 Same as above.] [Section 26] Use of a compound represented by general formula (1) for producing one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, and polyester polyol resins. [Section 27] A method in which a compound represented by general formula (1) is used as a monomer (a raw material) of one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic ester resins, polymethacrylic ester resins, and polyester polyol resins. [Section 28] Use of a compound represented by general formula (1) as a monomer for modifying one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, and polyester polyol resins. [Section 29] A method for modifying one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic ester resins, polymethacrylic ester resins, and polyester polyol resins, using a monomer containing a compound represented by general formula (1). Effect of the Invention

[0010] The compound represented by the general formula (1) (cyclic diol compound) is useful as a modifier or raw material monomer for resins having polyester bonds, polyurethane bonds, polycarbonate bonds, etc. The compound represented by the general formula (1a) and the compound represented by the general formula (1c) are novel compounds and are useful as modifiers or raw materials for the resins.

[0011] Resins (e.g., polyester carbonate resins, polycarbonate resins, etc.) obtained using the resin modifier of the present invention are characterized by their large refractive index, and thus the refractive index of the resulting resin can be adjusted over a wide range by adjusting the content of the resin modifier in the monomer. In addition, the resin modifier of the present invention can be copolymerized with various dihydroxy compounds in an appropriate ratio to make the birefringence of the resulting resin as close to zero as possible, and therefore the resin can be suitably used for optical applications (optical lenses, optical films, optical sheets, etc.). [Brief description of the drawings]

[0012] [Figure 1] 1 is an IR spectrum of isophthalaldehyde trimethylolethane diacetal (Compound 1) obtained in Example 1. [Diagram 2] 1 is a 1H-NMR spectrum of isophthalaldehyde trimethylolethane diacetal (compound 1) obtained in Example 1. [Diagram 3] 1 is an IR spectrum of isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2. [Figure 4] 1 is a 1H-NMR spectrum of isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2. [Diagram 5] 1 is an IR spectrum of terephthalaldehyde trimethylolethane diacetal (compound 3) obtained in Example 3. [Figure 6]1 is a 1H-NMR spectrum of terephthalaldehyde trimethylolethane diacetal (compound 3) obtained in Example 3. [Figure 7] 1 is an IR spectrum of terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4. [Figure 8] 1 is a 1H-NMR spectrum of terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4. [Figure 9] 1 is an IR spectrum of ortho-phthalaldehyde trimethylolethane diacetal (Compound 5) obtained in Example 5. [Figure 10] 1 is a 1H-NMR spectrum of ortho-phthalaldehyde trimethylolethane diacetal (compound 5) obtained in Example 5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 1.Resin modifier The resin modifier of the present invention comprises a compound represented by general formula (1). [ka] [In the formula, R 1 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms. Ring A represents a benzene ring optionally substituted with 1 to 4 groups selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.]

[0014] In the general formula (1), R 1 are preferably the same or different and each is preferably a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group. 1The linear or branched alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, preferred are a methyl group, an ethyl group, an isobutyl group, and a tert-butyl group. More preferred are a methyl group and an ethyl group. Particularly preferred is a methyl group.

[0015] In the general formula (1), ring A means that two acetal groups are bonded to each other at the ortho, meta or para position on the benzene ring. Specifically, ring A includes the following structures. [ka] [In the formula, ring A is the same as above.]

[0016] In general formula (1), ring A is preferably a benzene ring optionally substituted with 1 to 4 groups selected from the group consisting of linear or branched alkoxy groups having 1 to 6 carbon atoms and linear or branched alkyl groups having 1 to 6 carbon atoms.

[0017] The "straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms" as the substituent is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, etc. Among these, preferred are a methoxy group, an ethoxy group, an isopropyloxy group, an isobutyloxy group, and a tert-butyloxy group.

[0018] The "straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms" as the substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. Among these, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a tert-butyl group are preferred.

[0019] Particularly preferred as ring A is a benzene ring having no substituent, that is, a divalent phenylene group having the following structure: [ka]

[0020] The compound represented by the general formula (1) is a hydroxymethyl group in the two acetal groups and R 1 Depending on the configuration of the carbon atom to which it is attached, multiple stereoisomers are possible. These isomers may be present alone or in mixture.

[0021] The resin to which the resin modifier of the present invention is applied is not particularly limited as long as it is a resin that can contain a repeating unit (constituent unit) derived from a cyclic diol compound represented by general formula (1), that is, a divalent repeating unit obtained by removing a hydrogen atom of a hydroxyl group from a cyclic diol compound represented by general formula (1), and examples thereof include resins having a polyester bond, a polycarbonate bond, a polyurethane bond, etc. in the molecule. Specific examples thereof include polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, polyester polyol resins, etc. Preferred are polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferred are polyester carbonate resins and polycarbonate resins.

[0022] Three compounds classified based on the substitution positions of the two acetal groups on ring A, which are included in the compounds represented by general formula (1), that is, the compounds represented by the following general formulae (1a), (1b), and (1c), will be specifically described.

[0023] The compound represented by general formula (1a) is as follows. [ka] [In the formula, R2 R are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. 1 Same as above.]

[0024] In general formula (1a), R 1 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. Of these, a methyl group, an ethyl group, an isobutyl group, or a tert-butyl group is preferred. In particular, a methyl group and an ethyl group are advantageous for the progress of the acetalization reaction from the viewpoint of steric hindrance.

[0025] In general formula (1a), R 2 is preferably a hydrogen atom, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms. 2 Particularly preferably, is a hydrogen atom. R 2 The "straight or branched alkoxy group having 1 to 4 carbon atoms" is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, etc. Among these, preferred are a methoxy group, an ethoxy group, an isopropyloxy group, an isobutyloxy group, and a tert-butyloxy group.

[0026] R 2 The "straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. Among these, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a tert-butyl group are preferred.

[0027] The compound represented by the general formula (1a) may have isomers such as isomer A, isomer B, or isomer C. These isomers may exist alone or in mixture. [ka] [In the formula, R 1 and R 2 Same as above.]

[0028] When the compound represented by the general formula (1a) is a mixture of two or more isomers, the isomer ratio can be determined by the area percentage method by performing gas chromatography (GC) analysis using the method described in the Examples. Each isomer usually has its own unique peak in GC analysis. The content ratio of the isomer can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage ratio of each isomer can be the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl group using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

[0029] The compound represented by the general formula (1a) may have isomers such as the above-mentioned isomer (1a-A), isomer (1a-B), or isomer (1a-C). The isomer peaks detected by GC analysis are two or three, and these are considered to be isomer (1a-A), isomer (1a-B), or isomer (1a-C). The isomer ratio by GC analysis can be in the range of isomer (1a-A):isomer (1a-B):isomer (1a-C) = 10 to 1:10 to 1:1.

[0030] Specific examples of the compound represented by the general formula (1a) include, for example, isophthalaldehyde trimethylolpropane diacetal, isophthalaldehyde trimethylolethane diacetal, 5-methylisophthalaldehyde trimethylolethane diacetal, 4-methylisophthalaldehyde trimethylolethane diacetal, 4-chloroisophthalaldehyde trimethylolethane diacetal, 5-chloroisophthalaldehyde trimethylolethane diacetal, 5 -Bromoisophthalaldehyde trimethylolethane diacetal, 4-Bromoisophthalaldehyde trimethylolethane diacetal, 2-Bromoisophthalaldehyde trimethylolethane diacetal, 4,6-Dimethylisophthalaldehyde trimethylolethane diacetal, 2,4-Dimethylisophthalaldehyde trimethylolethane diacetal, 2,5-Dichloroisophthalaldehyde trimethylolethane diacetal, 4,6-Dichloroisophthalaldehyde isophthalaldehyde trimethylolethane diacetal, 4,6-dibromoisophthalaldehyde trimethylolethane diacetal, 2,5-dibromoisophthalaldehyde trimethylolethane diacetal, 5-tert-butylisophthalaldehyde trimethylolethane diacetal, 2,4,5,6-tetrafluoroisophthalaldehyde trimethylolethane diacetal, 5-(bromomethyl)isophthalaldehyde trimethylolethane diacetal, 4-isopropyl Isophthalaldehyde trimethylolethane diacetal, 4,6-diisopropylisophthalaldehyde trimethylolethane diacetal, 2-bromo-5-tert-butylisophthalaldehyde trimethylolethane diacetal, 4-phenylisophthalaldehyde trimethylolethane diacetal, 5-phenylisophthalaldehyde trimethylolethane diacetal, 4-phenyl-6-methylisophthalaldehyde trimethylolethane diacetal, 4,5-Diethyl-6-methylisophthalaldehyde trimethylolethane diacetal, 5-Hexylisophthalaldehyde trimethylolethane diacetal, 4-Hexylisophthalaldehyde trimethylolethane diacetal, 5-Butyloxyisophthalaldehyde trimethylolethane diacetal, 2-Methoxyisophthalaldehyde trimethylolethane diacetal, 4-Methoxyisophthalaldehyde trimethylolethane diacetal, 5-Methoxyisophthalaldehyde trimethylolethane diacetal, 2-Methoxy -4-Methylisophthalaldehyde trimethylolethane diacetal, 2-Methyl-4-methoxyisophthalaldehyde trimethylolethane diacetal, 2-Methoxy-5-methylisophthalaldehyde trimethylolethane diacetal, 4-Methyl-6-methoxyisophthalaldehyde trimethylolethane diacetal, 4,6-Dimethoxyisophthalaldehyde trimethylolethane diacetal, 2-Methoxy-4-ethylisophthalaldehyde trimethylolethane diacetal, 4,6-Dimethyl-2-Methoxyisophthalaldehyde 2,4-Dimethoxy-6-Methylisophthalaldehyde Trimethylolethane Diacetal, 2,4-Dimethyl-6-Methoxyisophthalaldehyde Trimethylolethane Diacetal, 4-Ethyl-5-Methyl-6-Methoxyisophthalaldehyde Trimethylolethane Diacetal, 5-Methylisophthalaldehyde Trimethylolpropane Diacetal, 4-Methylisophthalaldehyde Trimethylolpropane Diacetal, 4-Chloroisophthalaldehyde Trimethylolpropane Diacetal Tar, 5-chloroisophthalaldehyde trimethylolpropane diacetal, 5-bromoisophthalaldehyde trimethylolpropane diacetal, 4-bromoisophthalaldehyde trimethylolpropane diacetal, 2-bromoisophthalaldehyde trimethylolpropane diacetal, 4,6-dimethylisophthalaldehyde trimethylolpropane diacetal, 2,4-dimethylisophthalaldehyde trimethylolpropane diacetal, 2,5-dichloroisophthalaldehyde trimethylolpropane diacetal, 4,6-Dichloroisophthalaldehyde trimethylolpropane diacetal, 4,6-Dibromoisophthalaldehyde trimethylolpropane diacetal, 2,5-Dibromoisophthalaldehyde trimethylolpropane diacetal, 5-tert-butylisophthalaldehyde trimethylolpropane diacetal, 2,4,5,6-Tetrafluoroisophthalaldehyde trimethylolpropane diacetal, Acetal, 4-Isopropylisophthalaldehyde trimethylolpropane diacetal, 4,6-Diisopropylisophthalaldehyde isophthalaldehyde trimethylolpropane diacetal, 2-bromo-5-tert-butyl isophthalaldehyde trimethylolpropane diacetal, 4-phenyl isophthalaldehyde trimethylolpropane diacetal, 5-phenyl isophthalaldehyde trimethylolpropane diacetal, 4-phenyl-6-methyl isophthalaldehyde trimethylolpropane diacetal, 4,5-diethyl-6-methyl isophthalaldehyde trimethylolpropane diacetal, 5-hexyl isophthalaldehyde trimethylolpropane diacetal, 4-Hexylisophthalaldehyde trimethylolpropane diacetal, 5-Butyloxyisophthalaldehyde trimethylolpropane diacetal, 2-Methoxyisophthalaldehyde trimethylolpropane diacetal, 4-Methoxyisophthalaldehyde trimethylolpropane diacetal, 5-Methoxyisophthalaldehyde trimethylolpropane diacetal, 2-Methoxy-4-Methylisophthalaldehyde trimethylolpropane diacetal, 2-Methyl-4-Methoxyisophthalaldehyde trimethylolpropane diacetal Tar, 2-methoxy-5-methylisophthalaldehyde trimethylolpropane diacetal, 4-methyl-6-methoxyisophthalaldehyde trimethylolpropane diacetal, 4,6-dimethoxyisophthalaldehyde trimethylolpropane diacetal, 2-methoxy-4-ethylisophthalaldehyde trimethylolpropane diacetal, 4,6-dimethyl-2-methoxyisophthalaldehyde trimethylolpropane diacetal, 2,4-dimethoxy-6-methylisophthalaldehyde trimethylolpropane diacetal, 2,Examples of the compound include 4-dimethyl-6-methoxyisophthalaldehyde trimethylolpropane diacetal, 4-ethyl-5-methyl-6-methoxyisophthalaldehyde trimethylolpropane diacetal, etc. Among them, preferred compounds include isophthalaldehyde trimethylolpropane diacetal, isophthalaldehyde trimethylolethane diacetal, 5-methylisophthalaldehyde trimethylolethane diacetal, 5-methylisophthalaldehyde trimethylolpropane diacetal, 4-methylisophthalaldehyde trimethylolpropane diacetal, 4-methylisophthalaldehyde trimethylolethane diacetal, etc., and particularly preferred compounds include isophthalaldehyde trimethylolpropane diacetal, isophthalaldehyde trimethylolethane diacetal, etc.

[0031] The compound represented by general formula (1b) is as follows. [ka] [In the formula, R 1 and R 2 Same as above.]

[0032] Preferred R in formula (1b) 1 As for R in the general formula (1a), 1 In addition, preferred R in general formula (1b) is the same as 2 As for R in the general formula (1a), 2 is the same as:

[0033] The compound represented by the general formula (1b) may have isomers such as the following isomer (1b-A), isomer (1b-B), or isomer (1b-C). These isomers may exist alone or in mixture. [ka] [In the formula, R 1 and R 2 Same as above.]

[0034] When the compound represented by general formula (1b) is a mixture of two or more isomers, the isomer ratio can be determined by the area percentage method by performing gas chromatography (GC) analysis using the method described in the Examples. Each isomer usually has its own unique peak in GC analysis. The content ratio of the isomer can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage ratio of each isomer can be the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl group using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

[0035] The compound represented by the general formula (1b) may have isomers such as the above-mentioned isomer (1b-A), isomer (1b-B), or isomer (1b-C). The isomer peaks detected by GC analysis are two or three, and these are considered to be isomer (1b-A), isomer (1b-B), or isomer (1b-C). The isomer ratio by GC analysis can be in the range of isomer (1b-A):isomer (1b-B):isomer (1b-C) = 10 to 1:10 to 1:1.

[0036] Specific examples of the compound represented by the general formula (1b) include terephthalaldehyde trimethylolpropane diacetal, terephthalaldehyde trimethylolethane diacetal, 2-methylterephthalaldehyde trimethylolethane diacetal, 3-methylterephthalaldehyde trimethylolethane diacetal, 3-chloroterephthalaldehyde trimethylolethane diacetal, 2-chloro ... Trimethylolethane diacetal, 2-bromoterephthalaldehyde trimethylolethane diacetal, 3-bromoterephthalaldehyde trimethylolethane diacetal, 3,6-dimethylterephthalaldehyde trimethylolethane diacetal, 2,3-dimethylterephthalaldehyde trimethylolethane diacetal, 2,5-dichloroterephthalaldehyde trimethylolethane diacetal, 3,6-dichloroterephthalaldehyde Terephthalaldehyde trimethylol ethane diacetal, 3,6-dibromoterephthalaldehyde trimethylol ethane diacetal, 2,5-dibromoterephthalaldehyde trimethylol ethane diacetal, 2-tert-butylterephthalaldehyde trimethylol ethane diacetal, 2,3,5,6-tetrafluoroterephthalaldehyde trimethylol ethane diacetal, 3-isopropylterephthalaldehyde trimethylol Ethane diacetal, 3,6-diisopropyl terephthalaldehyde trimethylol ethane diacetal, 2-bromo-5-tert-butyl terephthalaldehyde trimethylol ethane diacetal, 3-phenyl terephthalaldehyde trimethylol ethane diacetal, 2-phenyl terephthalaldehyde trimethylol ethane diacetal, 3-phenyl-6-methyl terephthalaldehyde trimethylol ethane diacetal, 3,5-Diethyl-6-methylterephthalaldehyde trimethylolethane diacetal, 2-Hexylterephthalaldehyde trimethylolethane diacetal, 3-Hexylterephthalaldehyde trimethylolethane diacetal, 2-Butyloxyterephthalaldehyde trimethylolethane diacetal, 3-Methoxyterephthalaldehyde trimethylolethane diacetal, 2-Methoxyterephthalaldehyde trimethylolethane diacetal, 2-Methoxy-3-methylterephthalaldehyde trimethylolethane diacetal, 2- Methyl-3-methoxyterephthalaldehyde trimethylolethane diacetal, 2-methoxy-5-methylterephthalaldehyde trimethylolethane diacetal, 3-methyl-6-methoxyterephthalaldehyde trimethylolethane diacetal, 3,6-dimethoxyterephthalaldehyde trimethylolethane diacetal, 2-methoxy-3-ethylterephthalaldehyde trimethylolethane diacetal, 3,6-dimethyl-2-methoxyterephthalaldehyde trimethylolethane diacetal, 2,3-dimethoxy-6-methyl Terephthalaldehyde trimethylolethane diacetal, 2,3-dimethyl-6-methoxyterephthalaldehyde trimethylolethane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde trimethylolethane diacetal, 2-methylterephthalaldehyde trimethylolpropane diacetal, 3-methylterephthalaldehyde trimethylolpropane diacetal, 3-chloroterephthalaldehyde trimethylolpropane diacetal, 2-chloroterephthalaldehyde trimethylolpropane diacetal, 2 -Bromoterephthalaldehyde trimethylolpropane diacetal, 3-Bromoterephthalaldehyde trimethylolpropane diacetal, 3,6-Dimethylterephthalaldehyde trimethylolpropane diacetal, 2,3-Dimethylterephthalaldehyde trimethylolpropane diacetal, 2,5-Dichloroterephthalaldehyde trimethylolpropane diacetal, 3,6-Dichloroterephthalaldehyde trimethylolpropane diacetal, 3,6-Dibromoterephthalaldehyde trimethylolpropane diacetal, 2,5-Dibromoterephthalaldehyde trimethylolpropane diacetal, 2-tert-butylterephthalaldehyde trimethylolpropane diacetal, 2,3,5,6-tetrafluoroterephthalaldehyde trimethylolpropane diacetal, 3-isopropylterephthalaldehyde trimethylolpropane diacetal, 3,6-diisopropylterephthalaldehyde trimethylolpropane diacetal, 2-bromo-5-tert-butylterephthalaldehyde trimethylolpropane diacetal terephthalaldehyde trimethylolpropane diacetal, 3-phenyl terephthalaldehyde trimethylolpropane diacetal, 2-phenyl terephthalaldehyde trimethylolpropane diacetal, 3-phenyl-6-methyl terephthalaldehyde trimethylolpropane diacetal, 3,5-diethyl-6-methyl terephthalaldehyde trimethylolpropane diacetal, 2-hexyl terephthalaldehyde trimethylolpropane diacetal, 3-hexyl terephthalaldehyde trimethylol Terephthalaldehyde diacetal, 2-butyloxyterephthalaldehyde trimethylolpropane diacetal, 3-methoxyterephthalaldehyde trimethylolpropane diacetal, 2-methoxyterephthalaldehyde trimethylolpropane diacetal, 2-methoxy-3-methylterephthalaldehyde trimethylolpropane diacetal, 2-methyl-3-methoxyterephthalaldehyde trimethylolpropane diacetal, 3-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal Methylolpropane diacetal, 3,6-dimethoxyterephthalaldehyde trimethylolpropane diacetal, 2-methoxy-3-ethylterephthalaldehyde trimethylolpropane diacetal, 2-methoxy-5-methylterephthalaldehyde trimethylolpropane diacetal, 3,6-dimethyl-2-methoxyterephthalaldehyde trimethylolpropane diacetal, 2,3-dimethoxy-6-methylterephthalaldehyde trimethylolpropane diacetal, 2,Examples of the compound include 3-dimethyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, etc. Among them, preferred compounds include terephthalaldehyde trimethylolpropane diacetal, terephthalaldehyde trimethylolethane diacetal, 2-methylterephthalaldehyde trimethylolethane diacetal, 2-methylterephthalaldehyde trimethylolpropane diacetal, 3-methylterephthalaldehyde trimethylolpropane diacetal, 3-methylterephthalaldehyde trimethylolethane diacetal, etc., and particularly preferred compounds include terephthalaldehyde trimethylolpropane diacetal, terephthalaldehyde trimethylolethane diacetal, etc.

[0037] The compound represented by general formula (1c) is as follows. [ka] [In the formula, R 1 and R 2 Same as above.]

[0038] Preferred R in formula (1c) 1 As for R in the general formula (1a), 1 In addition, preferred R in the general formula (1c) is the same as 2 As for R in the general formula (1a), 2 is the same as:

[0039] The compound represented by the general formula (1c) may have isomers such as the following isomer (1c-A), isomer (1c-B), or isomer (1c-C). These isomers may exist alone or in mixture. [ka] [In the formula, R 1 and R 2 Same as above.]

[0040] When the compound represented by the general formula (1c) is a mixture of two or more isomers, the isomer ratio can be determined by the area percentage method by performing gas chromatography (GC) analysis using the method described in the Examples. Each isomer usually has its own unique peak in GC analysis. The content ratio of the isomer can be expressed as the percentage of the peak area of ​​each isomer relative to the total peak area of ​​the cyclic diol compound. The percentage ratio of each isomer can be the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl group using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

[0041] The compound represented by the general formula (1c) may have isomers such as the above-mentioned isomer (1c-A), isomer (1c-B), or isomer (1c-C). The isomer peaks detected by GC analysis are two or three, which are considered to be isomer (1c-A), isomer (1c-B), or isomer (1c-C). The isomer ratio by GC analysis can be in the range of isomer (1c-A):isomer (1c-B):isomer (1c-C) = 10 to 1:10 to 1:1.

[0042] Specific examples of the compound represented by the general formula (1c) include, for example, orthophthalaldehyde trimethylolpropane diacetal, orthophthalaldehyde trimethylolethane diacetal, 3-methylorthophthalaldehyde trimethylolethane diacetal, 4-methylorthophthalaldehyde trimethylolethane diacetal, 3-chloroorthophthalaldehyde trimethylolethane diacetal, 3-bromoorthophthalaldehyde trimethylolethane diacetal, 3,6-dimethylorthophthalaldehyde trimethylolethane diacetal, Acetal, 3,4-Dimethyl orthophthalaldehyde trimethylol ethane diacetal, 3,5-Dimethyl orthophthalaldehyde trimethylol ethane diacetal, 4,5-Dimethyl orthophthalaldehyde trimethylol ethane diacetal, 3,6-Dichloro orthophthalaldehyde trimethylol ethane diacetal, 3,6-Dibromo orthophthalaldehyde trimethylol ethane diacetal, 3,6-Diethyl-4-Methyl orthophthalaldehyde trimethylol ethane diacetal, 3-Hexyl orthophthalaldehyde trimethylol ethane diacetal, 3-butyloxy orthophthalaldehyde trimethylol ethane diacetal, 3-methoxy orthophthalaldehyde trimethylol ethane diacetal, 3-methoxy-6-methyl orthophthalaldehyde trimethylol ethane diacetal, 3-methyl-6-methoxy orthophthalaldehyde trimethylol ethane diacetal, 3,6-dimethoxy orthophthalaldehyde trimethylol ethane diacetal, 3-methoxy-6-ethyl orthophthalaldehyde trimethylol ethane diacetal, 3,6-dimethyl-4- Methoxy orthophthalaldehyde trimethylolethane diacetal, 3,6-dimethoxy-4-methyl orthophthalaldehyde trimethylolethane diacetal, 3-methyl orthophthalaldehyde trimethylolpropane diacetal, 4-methyl orthophthalaldehyde trimethylolpropane diacetal, 3-chloro orthophthalaldehyde trimethylolpropane diacetal, 3-bromo orthophthalaldehyde trimethylolpropane diacetal, 3,6-dimethyl orthophthalaldehyde trimethylolpropane diacetal, 3,4-Dimethyl orthophthalaldehyde trimethylolpropane diacetal, 3,5-Dimethyl orthophthalaldehyde trimethylolpropane diacetal, 4,5-Dimethyl orthophthalaldehyde trimethylolpropane diacetal, 3,6-Dichloro orthophthalaldehyde trimethylolpropane diacetal, 3,6-Dibromo orthophthalaldehyde trimethylolpropane diacetal, 3,6-Diethyl-4-Methyl orthophthalaldehyde trimethylolpropane diacetal Pan diacetal, 3-hexyl orthophthalaldehyde trimethylolpropane diacetal, 3-butyloxy orthophthalaldehyde trimethylolpropane diacetal, 3-methoxy orthophthalaldehyde trimethylolpropane diacetal, 3-methoxy-6-methyl orthophthalaldehyde trimethylolpropane diacetal, 3-methyl-6-methoxy orthophthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxy orthophthalaldehyde orthophthalaldehyde trimethylolpropane diacetal, 3-methoxy-6-ethyl orthophthalaldehyde trimethylolpropane diacetal, 3,6-dimethyl-4-methoxy orthophthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxy-4-methyl orthophthalaldehyde trimethylolpropane diacetal, among which preferred compounds are orthophthalaldehyde trimethylolpropane diacetal and orthophthalaldehyde trimethylolethane diacetal. Examples of the compounds include 3-methyl orthophthalaldehyde trimethylolethane diacetal, 3-methyl orthophthalaldehyde trimethylolpropane diacetal, 4-methyl orthophthalaldehyde trimethylolpropane diacetal, and 4-methyl orthophthalaldehyde trimethylolethane diacetal. Particularly preferred compounds include orthophthalaldehyde trimethylolpropane diacetal and orthophthalaldehyde trimethylolethane diacetal.

[0043] 2. Manufacturing method of resin modifier The method for producing the compound represented by general formula (1) is not particularly limited, and for example, as shown in the following <Reaction Scheme 1>, the compound can be produced via a step of reacting a compound represented by general formula (3) with a compound represented by general formula (4) (acetalization reaction). [ka] [In the formula, R 1 and ring A is the same as above.] Specifically, the compound represented by general formula (1) can be produced by reacting a compound represented by general formula (3) with a compound represented by general formula (4) in the presence of an acid catalyst (acetalization reaction).

[0044] The reaction can usually be carried out in a solvent (e.g., toluene, etc.). The solvent can be heated and refluxed, and the reaction can be carried out while removing the generated water by azeotropic distillation with the solvent. The acid catalyst is not particularly limited as long as it has a catalytic effect, and a known acid catalyst can be used. For example, mineral 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, and trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, silica alumina, and heteropolyacids (e.g., phosphotungstic acid, phosphomolybdic acid, etc.); and various Lewis acids. The amount of the compound represented by formula (4) used is usually about 0.5 to 3 mol, and preferably about 0.8 to 2 mol, per mol of the compound represented by formula (3).

[0045] The compounds represented by general formula (1a), (1b), and (1c), which are included in the compounds represented by general formula (1), can also be produced in the same manner as in <Reaction Scheme 1>. The compound represented by general formula (1a) can be produced by reacting a compound represented by general formula (3a) with a compound represented by general formula (4) in the presence of an acid catalyst (acetalization reaction), as shown in the following <Reaction Scheme 2>. [ka] [In the formula, R 1 and R 2 Same as above.]

[0046] The compound represented by general formula (1b) can be produced by reacting a compound represented by general formula (3b) with a compound represented by general formula (4) in the presence of an acid catalyst (acetalization reaction), as shown in the following <Reaction Scheme 3>. [ka] [In the formula, R 1 and R 2 Same as above.]

[0047] The compound represented by general formula (1c) can be produced by reacting a compound represented by general formula (3c) with a compound represented by general formula (4) in the presence of an acid catalyst (acetalization reaction), as shown in the following <Reaction Scheme 4>. [ka] [In the formula, R 1 and R 2 Same as above.]

[0048] 3. Manufacturing resin using resin modifier The compound (cyclic diol compound) represented by the general formula (1) can be used as a raw material monomer for producing a resin, and can be polymerized alone or in combination with other monomers to produce a resin containing a repeating unit (structural unit) represented by the general formula (2). Examples of the resin include the above-mentioned resins having polyester bonds, polycarbonate bonds, polyurethane bonds, etc. in the molecule. Specific examples include polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic acid ester resins, polymethacrylic acid ester resins, polyester polyol resins, etc. Preferred examples include polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferred examples are polyester carbonate resins and polycarbonate resins.

[0049] When the resin is a polyester carbonate resin or a polycarbonate resin, it preferably contains a repeating unit (structural unit) represented by the following general formula (2). [ka] [In the formula, R 1 and ring A is the same as above.]

[0050] In the general formula (2), R 1 Specific and preferred examples of ring A are R 1 and are the same as specific and preferred examples of ring A.

[0051] The compounds represented by general formulae (1a), (1b), and (1c), which are included in the compounds represented by general formula (1), can be polymerized in the same manner, either alone or in combination with other monomers, to produce polyester carbonate resins or polycarbonate resins containing repeating units (structural units) represented by the following general formulae (2a), (2b), or (2c), respectively. [ka] [In the formula, R 1 and R 2 Same as above.]

[0052] [ka] [In the formula, R 1 and R 2 Same as above.]

[0053] [ka] [In the formula, R 1 and R 2 Same as above.]

[0054] A polycarbonate resin containing a repeating unit (structural unit) represented by general formula (2) can be produced by (polymerizing) a raw material monomer containing a compound represented by general formula (1) with a carbonyl precursor compound.

[0055] The compound represented by general formula (1) can be used alone as a raw material monomer for polycarbonate resin. The resulting polycarbonate resin is a homopolymer obtained by polymerizing only the compound represented by general formula (1) with a carbonyl precursor compound, and is composed of only the constitutional unit represented by general formula (2). As such a homopolymer, a homopolymer having a constitutional unit represented by general formula (2a) or a constitutional unit represented by general formula (2c) is preferable.

[0056] The raw material monomer of the polycarbonate resin may contain a dihydroxy compound generally used as a structural unit of the polycarbonate resin in addition to the compound represented by the general formula (1). Examples of the dihydroxy compound include an aliphatic dihydroxy compound and an aromatic dihydroxy compound.

[0057] That is, the polycarbonate resin may be a copolymer containing a structural unit derived from a general dihydroxy compound in addition to the structural unit represented by general formula (2) derived from the compound represented by general formula (1). The copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

[0058] Aliphatic dihydroxy compounds include a variety of compounds, particularly 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-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and the like.

[0059] Examples of aromatic dihydroxy compounds include various compounds, particularly 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)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, etc. In addition, examples include hydroquinone, resorcinol, and catechol.

[0060] The ratio of the compound represented by formula (1) in the raw material monomer used is not particularly limited, and is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total amount of monomers. That is, in the polycarbonate resin, the ratio of the constitutional unit represented by formula (2) derived from the compound represented by formula (1) is not particularly limited, and is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total constitutional units.

[0061] Examples of carbonyl precursor compounds include phosgene, triphosgene, diphenyl carbonate, and the like.

[0062] In addition to the compound represented by the general formula (1), the raw material monomer of the polyester carbonate resin may contain a dihydroxy compound, a dicarboxylic acid compound, a dicarboxylic anhydride compound, a hydroxycarboxylic acid compound, a hydroxycarboxylic acid ester compound, a dicarboxylic acid ester compound, etc., which are generally used as a structural unit of the polyester carbonate resin. Examples of the dihydroxy compound include the above-mentioned aliphatic dihydroxy compounds and aromatic dihydroxy compounds. For example, the raw material monomer is preferably one containing a structural unit derived from at least one monomer selected from the following monomer group. [ka] [In the formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a monovalent group obtained by removing one hydroxyl group from an alkylene glycol having 2 to 5 carbon atoms.]

[0063] That is, the polyester carbonate resin may contain, in addition to the structural unit represented by general formula (2) derived from the compound represented by general formula (1), structural units derived from general dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. The copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

[0064] The number average molecular weight (Mn) of the polycarbonate resin or polyester carbonate resin containing the constitutional unit represented by the general formula (2) is about 4000 to 100,000, preferably about 10000 to 50000, the weight average molecular weight (Mw) is about 5000 to 100,000, preferably about 6000 to 80000, and the polydispersity (Mw / Mn) is about 1 to 5, preferably about 1.5 to 4.5. The glass transition temperature (Tg) is about 100 to 200°C, preferably about 120 to 160°C.

[0065] The refractive index (n D ) is relatively large, and is usually 1.500 to 1.750, and preferably 1.520 to 1.650. The refractive index is a value measured by the method described in the Examples.

[0066] The Abbe number (ν d ) is usually 20.0 to 55.0, and preferably 24.0 to 45.0. The Abbe number is a value measured by the method described in the examples.

[0067] 4. Applications of modified resins The compound represented by the general formula (1) can be used as a single monomer or as a copolymerization monomer and polymerized to modify the properties of the resin. For example, the refractive index, birefringence, and other properties of the resin can be adjusted by adjusting the amount of the compound represented by the general formula (1) added and copolymerizing it with other monomers.

[0068] Therefore, the resin obtained by using the resin modifier of the present invention can be suitably used for optical members, for example. Optical members include, but are not limited to, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, etc. The resin of the present invention can be molded by a casting method with high flow, and is therefore particularly suitable for the manufacture of thin optical members. In a preferred embodiment of the present invention, optical members manufactured by using the resin of the present invention include optical lenses, optical films, optical sheets, etc.

[0069] The resin of the present invention can be suitably used for optical lenses. Optical lenses manufactured using the resin of the present invention (particularly, polycarbonate resin) have a high refractive index and excellent heat resistance, and therefore can be used in fields where expensive high refractive index glass lenses have been used in the past, such as telescopes, binoculars, and television projectors, and are extremely useful.

[0070] Furthermore, by adjusting the content of the structural unit derived from the compound represented by general formula (1) in the resin of the present invention, the refractive index of the resin can be adjusted over a wide range in accordance with the design of various optical lenses.

[0071] The resin of the present invention can be suitably used for optical films. Optical films produced using the resin of the present invention (particularly, polycarbonate resin) have excellent transparency and heat resistance, and are therefore suitably used for liquid crystal substrate films, optical memory cards, and the like.

[0072] The birefringence of the resin of the present invention can be made as close to zero as possible by adjusting the content of the structural unit derived from the compound represented by general formula (1). Generally, birefringence observed in resins for optical components obtained by polymerization can be classified into orientation birefringence, stress birefringence, and form birefringence. Among them, form birefringence is observed when fine fibrous materials in the resin are aligned, and can usually be ignored as an optical property of resins for optical components. Orientation birefringence is caused by molecular orientation, and stress birefringence is caused by residual stress during molding.

[0073] Resins for optical components have large birefringence, which leads to large optical distortion, and therefore problems such as bleeding and blurring can occur when used for optical lenses. For this reason, there is a demand for smaller birefringence to provide clearer vision.

[0074] There are various resins commonly used for optical components, among which polyester resins, polyester carbonate resins, polycarbonate resins, etc. can be mentioned. In particular, polyester carbonate resins and polycarbonate resins are excellent in transparency, impact resistance, heat resistance, dimensional stability, etc.

[0075] More specifically, a resin (particularly a polycarbonate resin) homopolymerized or copolymerized using a compound represented by general formula (1) has a property that the birefringence strength increases in the order of general formula (1c), general formula (1a), and general formula (1b). These compounds are excellent at adjusting the birefringence strength of the resin, and a resin having a birefringence close to zero can be produced by copolymerizing a structural unit derived from the compound represented by general formula (1) with a structural unit of another dihydroxy compound. The resin can be suitably used for applications requiring a birefringence close to zero, particularly as an optical member such as an optical lens, an optical film, or an optical sheet. Applicable optical members are not particularly limited, but examples thereof include a lens for a smartphone camera, a lens for an in-vehicle camera, a lens for goggles for VR (virtual reality) or MR (mixed reality), and a lens for a security camera.

[0076] In this specification, the expressions "comprise" and "contain" encompass the meanings of "consisting essentially of" and "consisting only of". EXAMPLES

[0077] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, various measurements of the cyclic diol compound were performed by the following methods. Reagents were used for compounds not specifically mentioned.

[0078] <Compound used> Isophthalaldehyde: Tokyo Chemical Industry Co., Ltd. Terephthalaldehyde: Tokyo Chemical Industry Co., Ltd. Ortho-phthalaldehyde: Tokyo Chemical Industry Co., Ltd. p-Toluenesulfonic acid monohydrate: Nacalai Tesque, Inc. Trimethylolethane and trimethylolpropane: manufactured by Tokyo Chemical Industry Co., Ltd. Bisphenoxyethanolfluorene (BPEF): manufactured by Tokyo Chemical Industry Co., Ltd. Diphenyl carbonate: Tokyo Chemical Industry Co., Ltd.

[0079] <Analysis by gas chromatography (GC)> The purity of the cyclic diol compound was determined by gas chromatography (GC) analysis under the following conditions and method, and the purity was determined by the area percentage method. (Sample preparation) 50 ml of methanol was added to 0.5 g of the cyclic diol compound and the mixture was shaken at room temperature to prepare a methanol solution of the cyclic diol compound, which was used as a sample for analysis.

[0080] [Measurement conditions] Equipment: Shimadzu GC-2020 Column: Agilent Technologies DB-1 30m x 0.25mm x 0.25μm Column temperature: 80℃ (holding time 5 min) - heating rate 10℃ / min - 320℃ (holding time 5 min) Injection temperature / detector temperature: 300℃ / 325℃ Split ratio: 30 Column flow rate: 1.17 ml / min Purge flow rate: 10.0 ml / min Detector: FID Carrier gas: Helium Gas linear velocity: 30cm / sec Injection volume: 1μl

[0081] <Melting point> The melting points of the cyclic diol compounds were measured using a differential calorimeter DSC6220 manufactured by SII NanoTechnology. 10.7 mg of the sample was placed in an aluminum pan manufactured by the same company and sealed, and the temperature was raised from 30°C to 200°C at a rate of 10°C / min under a nitrogen flow of 50 ml / min, and an endothermic peak was observed. The temperature at the top of the peak was taken as the melting point.

[0082] <Infrared absorption spectrum (IR spectrum)> The IR spectrum of the cyclic diol compound was measured by the ATR (attenuated total reflection) method using an infrared spectrometer (Spectrum 400 manufactured by PerkinElmer Japan Co., Ltd.).

[0083] <Proton nuclear magnetic resonance spectrum ( 1 H-NMR) Cyclic diol compounds 1 H-NMR was performed by dissolving the sample in a deuterated solvent (deuterated chloroform or deuterated methanol) and then measuring the concentration of the sample in a nuclear magnetic resonance apparatus (DRX-500, manufactured by Bruker Corporation). 1 H-NMR (500 MHz) was used for measurement. In addition, 1 Solvents used in H-NMR measurements may show water peaks. The peak due to water contained in deuterated chloroform is around 1.56 ppm, and the peak due to water contained in deuterated methanol is around 4.87 ppm.

[0084] <Glass transition temperature> The glass transition temperature of the obtained polycarbonate resin was measured using a differential calorimeter DSC6220 manufactured by SII NanoTechnology Co., Ltd. 6.7 mg of the sample was placed in an aluminum pan manufactured by the same company and sealed, and heated 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 heating rate of 10°C / min, and heated from 30°C to 220°C at a heating rate of 10°C / min. The inflection point in the 2nd run was taken as the glass transition temperature.

[0085] <Number average molecular weight, weight average molecular weight and polydispersity index> Approximately 30 mg of polycarbonate resin was dissolved in 8 ml of tetrahydrofuran to prepare a sample solution for molecular weight measurement. The number average molecular weight Mn and weight average molecular weight Mw were determined by gel permeation chromatography (GPC) under the following measurement conditions: polystyrene equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity (Mw / Mn). (Measurement conditions) Equipment: Pump (Shimadzu Corporation LC-20AD type) Autosampler (Shimadzu Corporation SIL-20A HT type) Detector RI (Shimadzu Corporation RID-10A type) Column oven (Shimadzu Corporation CTO-20A model) Column: Shodex LF-802, 2 columns (Showa Denko K.K.) Eluent: Tetrahydrofuran (THF) manufactured by Nacalai Tesque, Inc., containing approximately 0.025% BHT Column temperature: 40℃ Flow rate: 1.0mL / min Injection volume: 100μl Analysis method: PS equivalent molecular weight Standard polymer used: Shodex STANDARD SM-105

[0086] <Refractive index> The polycarbonate resin obtained in each of the manufacturing examples described below was heated in an amount of 0.8 g at 240°C under a pressure of 1 MPa for 1 minute in a compression molding machine manufactured by Shinto Metal Industries Co., Ltd., and then heated under a pressure of 20 MPa for 30 seconds, and then heated under a pressure of 10 MPa for 1 minute and 30 seconds. After cooling for 3 minutes, a polycarbonate film having a thickness of 0.1 mm was obtained. A rectangular test piece 40 mm long and 8 mm wide was cut out from this 0.1 mm thick film to serve as a measurement sample. The refractive index n was measured using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. according to the method of JIS-K-7142, using an interference filter with a wavelength of 589 nm (D line). D The measurement was performed using diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) as an intermediate solution.

[0087] <Total light transmittance> The 0.1 mm thick film prepared by the method described above in "Refractive Index" was used as the measurement sample, and the total light transmittance was measured using a Nippon Denshoku HazeMater NDH7000SPII according to the method of JIS-K-7136. The measurement was performed on three pieces of film, and the average of the actual values ​​obtained in these measurements was used as the measured value.

[0088] <Abbe number> A rectangular test piece 40 mm long and 8 mm wide was cut out from the 0.1 mm thick film prepared by the method described above for refractive index, and used as a measurement sample. The refractive index n of each wavelength was measured using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd., using interference filters with wavelengths of 656 nm (C line), 589 nm (D line), and 486 nm (F line) according to the method of JIS-K-7142. C , n D , n F The Abbe number ν d asked for. vD = (nD-1) / (nF-nC) In the measurements, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the intermediate liquid.

[0089] <Birefringence> The sample was heated and uniaxially stretched using a solid viscoelasticity measuring device (UBM, S1000-DVE3) equipped with a tensile jig. After the stretching was stopped, the thermostatic chamber was opened and cooled with a blower. The retardation of the stretched film was measured at wavelengths of 449.9, 498.0, 548.0, 588.8, 628.8, and 751.0 nm using a HAYASHI-REPIC Co., Ltd. Luminous Ace LA-100USW light source and a retardation measuring device KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. The birefringence Δn was calculated from the retardation at a wavelength of 588.8 nm and the film thickness of the stretched film using the following formula. When the slow axis coincides with the stretching direction, Δn is shown as a positive value, and when the slow axis coincides with the perpendicular direction, Δn is shown as a negative value. Birefringence Δn = (Retardation at measurement wavelength 588.8 nm [nm]) / (Film thickness [mm] × 10 6 )

[0090] <Synthesis of cyclic diol compounds> [Example 1] Into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark with a condenser, 13.4 g (0.1 mol) of isophthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.22 mol) of trimethylolethane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added, and the mixture was heated and stirred under reflux conditions for approximately 6 hours while removing the generated water. The reaction mixture was returned to room temperature, neutralized with 1g of triethylamine, 59ml of toluene was distilled off under reduced pressure, 100g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off, and the crystals were first rinsed twice with 50ml of ion-exchanged water, then rinsed twice with 100ml of 60°C warm water. Finally, the crystals were rinsed twice with 50ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 80°C to obtain 26.7g (0.08mol) of isophthalaldehyde trimethylolethane diacetal (hereinafter referred to as Compound 1) with a purity of 99.7% (GC area percentage). The melting point of the crystals was 165.9°C. The obtained isophthalaldehyde trimethylolethane diacetal was analyzed by IR spectrum and 1The H-NMR spectrum was measured. The results are shown in Figures 1 and 2. From the following characteristic peaks shown in Figure 1 and Figure 2, it was confirmed that the product was isophthalaldehyde trimethylolethane diacetal.

[0091] IR(cm -1 ):653,690,714,803,891,962,982,1007,1024,1043,1100,1164,1378,2866,2955,3349

[0092] [Example 2] Into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark condenser, 13.4 g (0.1 mol) of isophthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 29.5 g (0.22 mol) of trimethylolpropane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added, and the mixture was heated and stirred under reflux conditions for approximately 8 hours while removing the generated water. The reaction mixture was returned to room temperature, neutralized with 1g of triethylamine, 60ml of toluene was distilled off under reduced pressure, 150g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off, and the crystals were first rinsed twice with 50ml of ion-exchanged water, then rinsed twice with 100ml of 60°C warm water. Finally, the crystals were rinsed twice with 50ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 80°C to obtain isophthalaldehyde trimethylolpropane diacetal with a purity of 92.7% (GC area percentage). The obtained crystals were dissolved by heating with the addition of 60g of isopropyl alcohol, and 40g of isopropyl alcohol was distilled off, followed by the addition of 100ml of water. The precipitated crystals were filtered off, rinsed twice with 50 ml of ion-exchanged water, and then dried under reduced pressure at 80°C to obtain 27.0 g (0.07 mol) of isophthalaldehyde trimethylolpropane diacetal (hereinafter referred to as compound 2) with a purity of 98.5% (GC area percentage). The melting point of the crystals was 95.5°C. The obtained isophthalaldehyde trimethylolpropane diacetal was analyzed by IR spectrum and 1The H-NMR spectrum was measured. The results are shown in Figures 3 and 4. From the following characteristic peaks shown in Figure 3 and Figure 4, it was confirmed that the compound was isophthalaldehyde trimethylolpropane diacetal.

[0093] IR(cm -1 ):712,803,933,971,1030,1101,1165,1377,2859,2962,3374

[0094] [Example 3] Into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark with a condenser, 13.4 g (0.1 mol) of terephthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.22 mol) of trimethylolethane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added, and the mixture was heated and stirred under reflux conditions for approximately 6 hours while removing the generated water. The reaction mixture was returned to room temperature, neutralized with 1g of triethylamine, 50ml of toluene was distilled off under reduced pressure, 100g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off, and the crystals were rinsed twice with 50ml of ion-exchanged water, and then rinsed twice with 50ml of 60°C warm water. The wet crystals were dried under reduced pressure at 100°C to obtain 30.4g (0.09mol) of terephthalaldehyde trimethylolethane diacetal (hereinafter referred to as compound 3) with a purity of 99.7% (GC area percentage). The melting point of the crystals was 247.3°C. The IR spectrum and 1 The H-NMR spectrum was measured. The results are shown in Figures 5 and 6. From the following characteristic peaks shown in Figure 5 and Figure 6, it was confirmed that the product was terephthalaldehyde trimethylolethane diacetal.

[0095] IR(cm -1 ):656,778,804,918,964,977,993,1016,1042,1094,1374,2844,2933,2959,3413

[0096] [Example 4] Into a 500 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark condenser, 13.4 g (0.1 mol) of terephthalaldehyde, 0.67 g of p-toluenesulfonic acid monohydrate, 26.4 g (0.2 mol) of trimethylolpropane, 60 ml of toluene, and 60 ml of N,N-dimethylformamide were added, and the mixture was heated and stirred under reflux conditions for approximately 10 hours while removing the generated water. The reaction mixture was returned to room temperature, neutralized with 1g of triethylamine, 50ml of toluene was distilled off under reduced pressure, 150g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off, and the obtained crystals were first rinsed twice with 50ml of ion-exchanged water, and then rinsed twice with 50ml of 60°C warm water. The wet crystals were dried under reduced pressure at 100°C to obtain terephthalaldehyde trimethylolpropane diacetal with a purity of 96.9% (GC area percentage). The obtained crystals were dissolved by heating with the addition of 140g of isopropyl alcohol, and the precipitated crystals were filtered off after distilling off the isopropyl alcohol. The crystals were rinsed twice with 50ml of ion-exchanged water, and the wet crystals were dried under reduced pressure at 100°C to obtain 30.0g (0.08mol) of terephthalaldehyde trimethylolpropane diacetal with a purity of 97.0% (GC area percentage) (hereinafter referred to as Compound 4). The melting point of the crystals was 187.2°C. The IR spectrum and 1 The H-NMR spectrum was measured. The results are shown in Figures 7 and 8. From the following characteristic peaks shown in Figure 7 and Figure 8, it was confirmed that the product was terephthalaldehyde trimethylolpropane diacetal.

[0097] IR(cm -1 ):801,971,1000,1018,1099,1379,2855,2928,2967,3355

[0098] [Example 5] A 1000 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark condenser was charged with 40.2 g (0.3 mol) of ortho-phthalaldehyde, 1.0 g of p-toluenesulfonic acid monohydrate, 75.6 g (0.63 mol) of trimethylolethane, 180 ml of xylene, and 180 ml of N-methylpyrrolidone, and the mixture was heated and stirred under reflux conditions for approximately 4 hours while removing the generated water. After distilling off 170 ml of xylene under reduced pressure, the reaction mixture was returned to room temperature and neutralized with 25 ml of saturated sodium bicarbonate, after which 400 g of ion-exchanged water was added. 100 ml of ethyl acetate was added, and the organic layer and the aqueous layer were separated using a separatory funnel. 100 ml of ethyl acetate was added to the separated aqueous layer, and the operation of separating the organic layer and the aqueous layer was repeated twice in total. The organic layer obtained was concentrated using a rotary evaporator. The obtained crystals were ortho-phthalaldehyde trimethylolethane diacetal (hereinafter referred to as compound 5) with a purity of 99.2% (GC area percentage), 90.2 g (0.27 mol). The obtained ortho-phthalaldehyde trimethylolethane diacetal was analyzed by IR spectrum and 1 The H-NMR spectrum was measured. The results are shown in Figures 9 and 10. From the following characteristic peaks shown in Figure 9 and Figure 10, it was confirmed that the compound was ortho-phthalaldehyde trimethylolethane diacetal.

[0099] IR(cm -1 ):663,698,760,920,948,969,1003,1021,1042,1082,1099,1203,1386,1455,2850,2955,3414

[0100] <Resin production and physical property evaluation> [Production Example 1] (Production of Polycarbonate Resin 1) 9.5 g (0.03 mol) of Compound 1 obtained in Example 1, 49.2 g (0.11 mol) of bisphenoxyethanol fluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 2.5 × 10 -2 283.29 μL (70.8 × 10-7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") was taken out. During the reaction, the by-product phenol was distilled off. The polycarbonate resin 1 taken out was pulverized, and the glass transition temperature was measured and found to be 148°C. The number average molecular weight Mn was 20240, the weight average molecular weight Mw was 34640, and the polydispersity Mw / Mn was 1.71. The refractive index was 1.619. The birefringence was +0.006×10 at a wavelength of 588.8 nm. -2 The Abbe number was 25.6. The total light transmittance was 90%. The results are shown in Table 1.

[0101] [Production Example 2] (Production of Polycarbonate Resin 2) Compound 1 obtained in Example 1 (7.6 g, 0.02 mol), bisphenoxyethanol fluorene (23.0 g, 0.05 mol), diphenyl carbonate (16.5 g, 0.08 mol), and 2.5 × 10 -2 30.2 μL (76.1 × 10 -8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 28 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") was taken out. During the reaction, phenol produced as a by-product was distilled off. The polycarbonate resin 2 taken out was pulverized, and the glass transition temperature was measured and found to be 143°C. The number average molecular weight Mn was 27,800, the weight average molecular weight Mw was 56,000, and the polydispersity Mw / Mn was 2.00. The refractive index was 1.610. The birefringence was +0.033×10 at a wavelength of 588.8 nm. -2 The Abbe number was 26.8. The total light transmittance was 90%. The results are shown in Table 1.

[0102] [Production Example 3] (Production of Polycarbonate Resin 3) The compound 1 obtained in Example 1 was 23.0 g (0.07 mol), bisphenoxyethanol fluorene was 29.8 g (0.07 mol), diphenyl carbonate was 29.9 g (0.14 mol), and 2.5 × 10 -2 54.9 μL (137.2 × 10 -8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 35 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") was taken out. During the reaction, phenol produced as a by-product was distilled off. The polycarbonate resin 3 taken out was pulverized, and the glass transition temperature was measured and found to be 145°C. The number average molecular weight Mn was 26,300, the weight average molecular weight Mw was 53,630, and the polydispersity Mw / Mn was 2.04. The refractive index was 1.588. The birefringence was +0.062×10 at a wavelength of 588.8 nm. -2 The Abbe number was 28.5. The total light transmittance was 90%. The results are shown in Table 1.

[0103] [Production Example 4] (Production of Polycarbonate Resin 4) Compound 1 obtained in Example 1 (15.4 g, 0.05 mol), diphenyl carbonate (10.0 g, 0.05 mol), and 2.5×10 -2 18.4 μL of sodium bicarbonate solution (46.0 × 10 -8mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 12 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 4") was taken out. During the reaction, phenol produced as a by-product was distilled off. The polycarbonate resin 4 taken out was pulverized, and the glass transition temperature was measured and found to be 127°C. The number average molecular weight Mn was 19920, the weight average molecular weight Mw was 51900, and the polydispersity Mw / Mn was 2.61. The refractive index was 1.525. The birefringence was +0.165×10 at a wavelength of 588.8 nm. -2 The Abbe number was 43.0. The total light transmittance was 92%. The results are shown in Table 1.

[0104] [Production Example 5] (Production of Polycarbonate Resin 5) The compound 2 obtained in Example 2 (10.4 g, 0.03 mol), bisphenoxyethanol fluorene (49.9 g, 0.11 mol), diphenyl carbonate (31.3 g, 0.15 mol), and 2.5 × 10 -2 286.9 μL (717.0 × 10 -8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") was taken out. During the reaction, phenol produced as a by-product was distilled off. The polycarbonate resin 5 taken out was pulverized, and the glass transition temperature was measured and found to be 132°C. The number average molecular weight Mn was 4350, the weight average molecular weight Mw was 7850, and the polydispersity Mw / Mn was 1.80. The refractive index was 1.620. The birefringence was +0.008×10 at a wavelength of 588.8 nm. -2 The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[0105] [Production Example 6] (Production of Polycarbonate Resin 6) 9.5 g (0.03 mol) of compound 3 obtained in Example 3, 49.2 g (0.11 mol) of bisphenoxyethanol fluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 2.5 × 10 -2 283.6 μL (70.9 × 10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 6") was taken out. During the reaction, the by-product phenol was distilled off. The polycarbonate resin 6 taken out was pulverized, and the glass transition temperature was measured and found to be 148°C. The number average molecular weight Mn was 18270, the weight average molecular weight Mw was 33430, and the polydispersity Mw / Mn was 1.83. The refractive index was 1.620. The birefringence was +0.013×10 at a wavelength of 588.8 nm. -2 The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[0106] [Production Example 7] (Production of Polycarbonate Resin 7) The compound 3 obtained in Example 3 (13.8 g, 0.04 mol), bisphenoxyethanol fluorene (41.8 g, 0.09 mol), diphenyl carbonate (30.0 g, 0.14 mol), and 2.5 × 10 -2 55.0 μL of sodium bicarbonate solution (137.5 × 10 -8mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 7") was taken out. During the reaction, phenol by-product was distilled off. The polycarbonate resin 7 taken out was pulverized, and the glass transition temperature was measured and found to be 152.2°C. The number average molecular weight Mn was 28570, the weight average molecular weight Mw was 73910, and the polydispersity Mw / Mn was 2.59. The refractive index was 1.610. The birefringence was +0.052×10 at a wavelength of 588.8 nm. -2 The Abbe number was 27.5. The total light transmittance was 90%. The results are shown in Table 1.

[0107] [Production Example 8] (Production of Polycarbonate Resin 8) The compound 4 obtained in Example 4 (10.6 g, 0.02 mol), bisphenoxyethanol fluorene (49.2 g, 0.11 mol), diphenyl carbonate (30.9 g, 0.15 mol), and 2.5 × 10 -2 283.5 μL (70.9 × 10 -7 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 8") was taken out. During the reaction, phenol by-product was distilled off. The polycarbonate resin 8 taken out was pulverized, and the glass transition temperature was measured and found to be 140°C. The number average molecular weight Mn was 11790, the weight average molecular weight Mw was 50470, and the polydispersity Mw / Mn was 4.28. The refractive index was 1.622. The birefringence was +0.014×10 at a wavelength of 588.8 nm. -2 The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[0108] [Production Example 9] (Production of Polycarbonate Resin 9) The compound 5 obtained in Example 5 (5.8 g, 0.02 mol), bisphenoxyethanol fluorene (30.3 g, 0.07 mol), diphenyl carbonate (19.1 g, 0.09 mol), and 2.5 × 10 -2 34.9 μL (87.3 × 10 -8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 25 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 9") was taken out. During the reaction, phenol produced as a by-product was distilled off. The polycarbonate resin 9 taken out was pulverized, and the glass transition temperature was measured and found to be 146.1°C. The number average molecular weight Mn was 15,400, the weight average molecular weight Mw was 39,800, and the polydispersity Mw / Mn was 2.58. The physical properties of the obtained polycarbonate film were measured. The refractive index was 1.619. The birefringence was −0.004×10 at a wavelength of 588.8 nm. -2 The Abbe number was 26.0. The total light transmittance was 89%. The results are shown in Table 1.

[0109] [Comparative Production Example 1] (Production of Polycarbonate Resin A) 59.0 g (0.13 mol) of bisphenoxyethanol fluorene, 30.0 g (0.14 mol) of diphenyl carbonate, and 2.5 × 10 -2 55.0 μL of sodium bicarbonate solution (137.5 × 10-8 mol) was placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200°C. After the substrate was dissolved, the temperature was gradually increased to 240° C. over 80 minutes, and the pressure was gradually reduced to 150 mmHg. The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after maintaining the pressure for 20 minutes, 55 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin A") was taken out. During the reaction, phenol, which was a by-product, was distilled off. The polycarbonate resin A taken out was pulverized, and the glass transition temperature was measured and found to be 147°C. The number average molecular weight Mn was 21940, the weight average molecular weight Mw was 41680, and the polydispersity Mw / Mn was 1.90.

[0110] The refractive index was 1.638. The birefringence was -0.023×10 at a wavelength of 588.8 nm. -2 The Abbe number was 23.5. The total light transmittance was 90%. The results are shown in Table 1. [Table 1]

[0111] From Production Examples 1 to 9 in Table 1, it was found that the polycarbonate resins obtained using Compounds 1 to 5 have a relatively high refractive index and a high Abbe number. It was also found that the birefringence strength of the resin increases in the order of Compound 5, Compound 1, and Compound 3 (the order of the compounds in which the substitution positions of the two acetal groups on the benzene ring are the ortho, meta, and para positions). For example, this can be easily understood by comparing the birefringence of the resins obtained in Production Examples 1, 6, and 9 at a copolymerization ratio (BPEF:cyclic diol compound) of 80:20. As a result, the compounds of the present invention can be appropriately selected and combined depending on the desired birefringence strength of the resin.

[0112] Comparison of Comparative Production Example 1 with Production Examples 1 to 4, and comparison of Comparative Production Example 1 with Production Examples 6 and 7 reveals that the refractive index, birefringence, and Abbe number of the resulting polycarbonate resin can be adjusted by changing the copolymerization ratio of Compound 1 or Compound 3 as the raw material monomer.

[0113] Compounds 1 and 2 (included in the compound represented by general formula (1a)) are useful because they have good optical properties such as refractive index, birefringence, and Abbe number, and good heat resistance represented by glass transition temperature, as well as because the raw materials are industrially easily available.

[0114] It was confirmed from Production Examples 6 and 7 that the glass transition temperature of the resin increases significantly as the copolymerization ratio of compound 3 increases. Therefore, the resin using compound 3 (included in the compound represented by general formula (1b)) is suitable for high heat resistance applications.

[0115] From Production Example 9, it is considered that the resin using compound 5 (included in the compound represented by general formula (1c)) has a relatively small birefringence intensity, and therefore has the advantage that it is easy to finely adjust the copolymerization ratio with the combined monomer in order to make the birefringence of the resin obtained by copolymerization zero. As a result, the birefringence of the resin can be made as close to zero as possible. [Industrial Applicability]

[0116] The cyclic diol compound of the present invention can be used as a raw material monomer and modifier for resins such as polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylic ester resins, and polymethacrylic ester resins. In particular, it is suitable for polycarbonate resins containing structural units derived from the cyclic diol compound. In addition, by using the cyclic diol compound of the present invention as a resin modifier, the physical properties such as glass transition temperature, refractive index, birefringence, and Abbe number of the resin can be widely adjusted. Therefore, it is suitable for use in optical materials such as optical lenses and optical films.

Claims

1. A resin modifier comprising a compound represented by general formula (1): The resin modifier is an agent used as a raw material monomer for a resin having a carbonate bond in the molecule, and modifies the physical properties of the resin. Resin modifier. 【Chemistry 1】 [In the formula, R １ are the same or different and represent a methyl group or an ethyl group. Ring A represents a benzene ring.

2. The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1a). 【Chemistry 2】 [In the formula, R ２ represents a hydrogen atom. １ is the same as above.]

3. The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1b). 【Chemistry 3】 [In the formula, R ２ represents a hydrogen atom. １ is the same as above.]

4. The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1c). 【Chemistry 4】 [In the formula, R ２ represents a hydrogen atom. １ is the same as above.]

5. The resin modifier of claim 1 , wherein the resin is a polycarbonate resin or a polyester carbonate resin.

6. The resin modifier according to claim 1 , wherein the resin is a resin used for optical members.

7. The resin modifier according to claim 6 , wherein the optical component is an optical lens, an optical film, or an optical sheet.

8. A compound represented by general formula (1a): 【Chemistry 5】 [In the formula, R １ are the same or different and represent a methyl group or an ethyl group. ２ represents a hydrogen atom.

9. A compound represented by general formula (1c): 【Chemistry 6】 [In the formula, R １ are the same or different and each represents a methyl group or an ethyl group. ２ represents a hydrogen atom.

10. A method for producing a compound represented by general formula (1a), comprising a step of reacting a compound represented by general formula (3a) with a compound represented by general formula (4). 【Chemistry 7】 [In the formula, R １ are the same or different and each represents a methyl group or an ethyl group. ２ represents a hydrogen atom.

11. A method for producing a compound represented by general formula (1c), comprising a step of reacting a compound represented by general formula (3c) with a compound represented by general formula (4). 【Chemistry 8】 [In the formula, R １ are the same or different and each represents a methyl group or an ethyl group. ２ represents a hydrogen atom.

12. Use of a compound represented by formula (1) as a raw material monomer for producing a resin having a carbonate bond in the molecule. 【Chemistry 9】 [In the formula, R １ are the same or different and represent a methyl group or an ethyl group. Ring A represents a benzene ring.

13. A method in which a compound represented by the general formula (1) is used as a raw material monomer for a resin having a carbonate bond in the molecule. 【Chemistry 10】 [In the formula, R １ are the same or different and represent a methyl group or an ethyl group. Ring A represents a benzene ring.

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