Cyclic diol compounds, methods for producing the compounds, and uses of the compounds

Abstract

The present application provides a modifier for resins such as polyester resins, polyester carbonate resins, and polycarbonate resins. In addition, the present application provides a cyclic diol compound useful as a resin modifier, and a method for producing the same. The present application relates to a resin modifier comprising a compound represented by general formula (1), and the like.[In the formula, R 1 The same or different, 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, and ring A represents a phenyl ring which can be 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.]

Description

Technical Field

[0001] This invention relates to cyclic diol compounds, methods for manufacturing the compounds, and uses of the compounds. Background Technology

[0002] Various cyclic diol compounds are known as resin raw materials for polyester and polycarbonate resins. Among the industrially available cyclic diol compounds are 1,4-cyclohexanediol, 1,4-cyclohexanediol, and 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A). Furthermore, various cyclic diol compounds have been reported depending on the intended use of the resin to be manufactured.

[0003] For example, regarding polycarbonate resins used for optical applications (such as optical lenses), in order to reduce coloration and improve the optical properties of the resin such as transparency, a method for manufacturing using a diol component containing a specific aromatic diol compound having a fluorene ring structure has been reported (Patent Document 1). In addition, a method for manufacturing using a specific fluorene-containing dihydroxy compound and other dihydroxy compounds in a specific ratio has been reported (Patent Document 2), etc.

[0004] However, the properties of resins such as polyester and polycarbonate resins vary depending on the specific application in which they are used, and cyclic diol compounds that can meet the resin properties required by these applications are being explored. In particular, when resins are used for optical applications, there is a need for cyclic diol compounds that can improve the optical properties of the resin.

[0005] Existing technical documents

[0006] Patent documents

[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] The problem that the invention aims to solve

[0010] The objective of this invention is to provide modifiers for resins such as polyester resins, polyester carbonate resins, and polycarbonate resins. Furthermore, another objective of this invention is to provide cyclic diol compounds useful as resin modifiers and methods for their manufacture.

[0011] Methods for solving problems

[0012] To address the aforementioned problems, the inventors conducted in-depth research and discovered that by adding a cyclic diol compound with a diacetal structure, as shown in formula (1), as a structural unit (repeating unit) to a resin, the physical properties of the resin can be modified to produce a resin with new physical properties. Specifically, this cyclic diol compound was found to be useful as a raw material (monomer) or modifier for resins such as polyester resin, polyester carbonate resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin, and polyester polyol resin. Based on this insight, further research was conducted, resulting in the present invention.

[0013] That is, the present invention provides the following resin modifier containing a cyclic diol compound, the cyclic diol compound, and a method for manufacturing the compound.

[0014] [Item 1]

[0015] A resin modifier comprising a compound represented by general formula (1) (hereinafter also referred to as a "cyclic diol compound").

[0016]

[0017] [In the formula, R] 1 Whether identical or different, each represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl group, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Ring A represents a benzene ring that may be substituted with 1 to 4 groups selected from the group consisting of a fluorine atom, chlorine atom, bromine atom, phenyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, and a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0018] [Item 2]

[0019] According to the resin modifier described in [Item 1], the resin modifier is a modifier of one or more resins selected from the group consisting of polyester resin, polyester carbonate resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin and polyester polyol resin.

[0020] [Item 3]

[0021] According to the resin modifier described in [Item 1] or [Item 2], wherein, in general formula (1), R 1 They may be the same or different, each being methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or phenyl.

[0022] [Item 4]

[0023] According to the resin modifier described in [Item 3], wherein, in general formula (1), R 1 They may be the same or different, each being either methyl or ethyl.

[0024] [Item 5]

[0025] According to any one of [Item 1] to [Item 4], in general formula (1), ring A is a benzene ring that can be substituted by 1 to 4 groups selected from the group consisting of a straight-chain or branched alkoxy group having 1 to 6 carbon atoms and a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0026] [Item 6]

[0027] The resin modifier according to any one of [Item 1] to [Item 5], wherein, in general formula (1), R 1 It is methyl or ethyl, and ring A is a benzene ring that can be substituted by 1 to 4 groups selected from the group consisting of methyl and ethyl.

[0028] [Item 7]

[0029] The resin modifier according to any one of [Item 1] to [Item 6], wherein, in general formula (1), ring A is a benzene ring.

[0030] [Item 8]

[0031] According to the resin modifier described in [Item 1] or [Item 2], wherein the compound represented by general formula (1) is the compound represented by general formula (1a).

[0032]

[0033] [In the formula, R] 2 Whether identical or different, each represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 Same as above.

[0034] [Item 9]

[0035] According to the resin modifier described in [Item 1] or [Item 2], wherein the compound represented by general formula (1) is the compound represented by general formula (1b).

[0036]

[0037] [In the formula, R] 1 and R 2 Same as above.

[0038] [Item 10]

[0039] According to the resin modifier described in [Item 1] or [Item 2], wherein the compound represented by general formula (1) is the compound represented by general formula (1c).

[0040]

[0041] [In the formula, R] 1 and R 2 Same as above.

[0042] [Item 11]

[0043] A monomer for resin raw materials comprising a compound represented by general formula (1).

[0044] [Item 12]

[0045] The compound represented by general formula (1a).

[0046]

[0047] [In the formula, R] 1 and R 2 Same as above.

[0048] [Item 13]

[0049] The compound represented by general formula (1c).

[0050]

[0051] [In the formula, R] 1 and R 2 Same as above.

[0052] [Item 14]

[0053] According to the compound described in [Item 12] or [Item 13], wherein R 1 They may be the same or different, each being methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or phenyl.

[0054] [Item 15]

[0055] According to the compound described in [Item 14], wherein R 1 They may be the same or different, each being either methyl or ethyl.

[0056] [Item 16]

[0057] The compound according to any one of [Item 12] to [Item 15], wherein R 2 Whether the groups are the same or different, each is a hydrogen atom, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0058] [Item 17]

[0059] The compound according to any one of [Item 12] to [Item 16], wherein R1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

[0060] [Item 18]

[0061] The compound according to any one of [Item 12] to [Item 17], wherein R 2 All are hydrogen atoms.

[0062] [Item 19]

[0063] A method for producing a compound of general formula (1) includes the step of reacting a compound of general formula (3) with a compound of general formula (4) (acetalization reaction).

[0064]

[0065] [In the formula, R] 1 And ring A is the same as described above.

[0066] [Item 20]

[0067] A method for producing a compound of general formula (1a) includes the step of reacting a compound of general formula (3a) with a compound of general formula (4) (acetalization reaction).

[0068]

[0069] [In the formula, R] 1 and R 2 Same as above.

[0070] [Item 21]

[0071] A method for manufacturing a compound of general formula (1c) includes a step of reacting the compound of general formula (3c) with the compound of general formula (4) (acetalization reaction).

[0072]

[0073] [In the formula, R] 1 and R 2 Same as above.

[0074] [Item 22]

[0075] A polycarbonate resin containing structural units (repeating units) represented by general formula (2).

[0076]

[0077] [In the formula, R] 1And ring A is the same as described above.

[0078] [Item 23]

[0079] The polycarbonate resin according to [item 22] contains structural units (repeating units) represented by general formula (2a).

[0080]

[0081] [In the formula, R] 1 and R 2 Same as above.

[0082] [Item 24]

[0083] The polycarbonate resin according to [item 22] contains structural units (repeating units) represented by general formula (2c).

[0084]

[0085] [In the formula, R] 1 and R 2 Same as above.

[0086] [Item 25]

[0087] The polycarbonate resin according to [item 22] contains structural units (repeating units) represented by general formula (2b).

[0088]

[0089] [In the formula, R] 1 and R 2 Same as above.

[0090] [Item 26]

[0091] The use of the compound represented by general formula (1) in the manufacture of one or more resins selected from the group consisting of polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethyl methacrylate resins and polyester polyol resins.

[0092] [Item 27]

[0093] A method of using the compound represented by general formula (1) as a monomer (as a raw material) of one or more resins selected from the group consisting of polyester resin, polyester carbonate resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin and polyester polyol resin.

[0094] [Item 28]

[0095] The compound represented by general formula (1) is used as a monomer for modifying one or more resins selected from the group consisting of polyester resin, polyester carbonate resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin and polyester polyol resin.

[0096] [Item 29]

[0097] 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, polyacrylate resins, polymethyl methacrylate resins and polyester polyol resins using a monomer containing a compound of general formula (1).

[0098] Invention Effects

[0099] The compounds shown in general formula (1) (cyclic diol compounds) are useful as modifiers or raw material monomers for resins having polyester bonds, polyurethane bonds, polycarbonate bonds, etc. The compounds shown in general formula (1a) and general formula (1c) are new compounds and are useful as modifiers or raw materials for the aforementioned resins.

[0100] Resins obtained using the resin modifier of the present invention (e.g., polyester carbonate resin, polycarbonate resin, etc.) have a high refractive index. Therefore, by adjusting the content of this resin modifier in the monomer, the refractive index of the obtained resin can be adjusted over a wide range.

[0101] Furthermore, the resin modifier of the present invention, by copolymerizing with various dihydroxy compounds in appropriate proportions, enables the birefringence of the resulting resin to approach zero. Therefore, this resin is suitable for optical applications (optical lenses, optical films, optical sheets, etc.). Attached Figure Description

[0102] Figure 1 The image shows the IR spectrum of isophthalaldehyde trihydroxymethyl ethane diacetal (compound 1) obtained in Example 1.

[0103] Figure 2 The isophthalaldehyde trimethylolethane diacetate (compound 1) obtained in Example 1 1 H-NMR spectrum.

[0104] Figure 3 The image shows the IR spectrum of isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2.

[0105] Figure 4 The isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2 1 H-NMR spectrum.

[0106] Figure 5 The image shows the IR spectrum of terephthalaldehyde trihydroxymethyl ethane diacetal (compound 3) obtained in Example 3.

[0107] Figure 6 The terephthalaldehyde trimethylolethane diacetal (compound 3) obtained in Example 3 1 H-NMR spectrum.

[0108] Figure 7 The image shows the IR spectrum of terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4.

[0109] Figure 8 The terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4 1 H-NMR spectrum.

[0110] Figure 9 The image shows the IR spectrum of phthalaldehyde trihydroxymethyl ethane diacetal (compound 5) obtained in Example 5.

[0111] Figure 10 The phthalaldehyde trimethylolpropane diacetal (compound 5) obtained in Example 5 1 H-NMR spectrum. Detailed Implementation

[0112] 1. Resin modifier

[0113] The resin modifier of the present invention comprises a compound represented by general formula (1).

[0114]

[0115] [In the formula, R] 1 Whether identical or different, each represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl group, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. Ring A represents a benzene ring that may be substituted with 1 to 4 groups selected from the group consisting of a fluorine atom, chlorine atom, bromine atom, phenyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, and a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0116] In general formula (1), R 1 Whether the compounds are the same or different, each is preferably a straight-chain or branched alkyl or phenyl compound having 1 to 4 carbon atoms. As R 1 The alkyl group having 1 to 4 carbon atoms shown is either straight-chain or branched, and is not particularly limited. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these, methyl, ethyl, isobutyl, and tert-butyl are preferred. Methyl and ethyl are more preferred. Methyl is particularly preferred.

[0117] In 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 structure.

[0118]

[0119] [In the formula, ring A is the same as described above.]

[0120] In general formula (1), ring A is preferably a benzene ring that can be substituted by 1 to 4 groups selected from the group consisting of a straight-chain or branched alkoxy group having 1 to 6 carbon atoms and a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0121] There are no particular limitations on the "linear or branched alkoxy group having 1 to 6 carbon atoms" used as a substituent, and examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these, methoxy, ethoxy, isopropoxy, isobutoxy, and tert-butoxy are preferred.

[0122] There are no particular limitations on the "straight-chain or branched alkyl group having 1 to 6 carbon atoms" used as a substituent, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among them, methyl, ethyl, isopropyl, isobutyl, and tert-butyl are preferred.

[0123] As ring A, a benzene ring without substituents, i.e. a divalent phenylene ring having the following structure, is particularly preferred.

[0124]

[0125] The compound represented by general formula (1) is believed to be based on the hydroxymethyl group and R in the two acetal groups. 1 The configuration of the bonded carbon atoms results in multiple stereoisomers. These isomers can exist individually or as mixtures.

[0126] The resin used as the resin modifier of the present invention is not particularly limited as long as it contains repeating units (structural units) from the cyclic diol compound represented by general formula (1), that is, divalent repeating units obtained by removing hydrogen atoms of the hydroxyl group from the cyclic diol compound represented by general formula (1). Examples include resins having polyester bonds, polycarbonate bonds, polyurethane bonds, etc. within the molecule. Specifically, examples include polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethyl methacrylate resins, polyester polyol resins, etc. Polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins are preferred, and polyester carbonate resins and polycarbonate resins are more preferred.

[0127] The compounds included in the compound of general formula (1) are classified based on the substitution positions of the two acetal groups on ring A, namely the compounds shown in general formula (1a), general formula (1b) and general formula (1c) below.

[0128] The compounds represented by general formula (1a) are shown below.

[0129]

[0130] [In the formula, R] 2 Whether identical or different, each represents a hydrogen atom, fluorine atom, chlorine atom, bromine atom, phenyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms. R 1 Same as above.

[0131] In general formula (1a), as R 1 Preferably, the alkyl group is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among these, methyl, ethyl, isobutyl, and tert-butyl are preferred. In particular, from a steric hindrance point of view, methyl and ethyl groups are favorable for the acetalization reaction.

[0132] In general formula (1a), as R 2 Preferably, it is an alkoxy group with hydrogen atoms and a straight-chain or branched structure having 1 to 6 carbon atoms, or an alkyl group with a straight-chain or branched structure having 1 to 6 carbon atoms. As R 2 The preferred atom is hydrogen.

[0133] As R 2 The term "alkoxy group with 1 to 4 carbon atoms in a straight or branched form" is not particularly limited, and examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among these, methoxy, ethoxy, isopropoxy, isobutoxy, and tert-butoxy are preferred.

[0134] As R 2 The term "alkyl group having 1 to 6 carbon atoms in a straight or branched form" is not particularly limited, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Among these, methyl, ethyl, isopropyl, isobutyl, and tert-butyl are preferred.

[0135] It is believed that the compound represented by general formula (1a) exists as isomers A, B, or C as described below. These isomers may be individual or in mixtures.

[0136]

[0137] [In the formula, R] 1 and R 2 Same as above.

[0138] When the compound represented by general formula (1a) is a mixture of two or more isomers, gas chromatography (GC) analysis can be performed using the method described in the examples, and the isomer ratio can be determined by the area percentage method. Each isomer typically exhibits its own unique peaks as determined by GC analysis. The proportion of isomers 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 ratio of the percentages of each isomer can be used as the isomer ratio. Alternatively, the cyclic diol compound of the present invention can be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0139] The compound represented by general formula (1a) is considered to exist as isomers such as (1a-A), (1a-B), or (1a-C) as described above. If two or three isomer peaks are detected in the GC analysis, these are considered to be isomers (1a-A), (1a-B), or (1a-C). The isomer ratio based on GC analysis can be in the range of isomer (1a-A): isomer (1a-B): isomer (1a-C) = 10–1:10–1:1.

[0140] Specific examples of compounds represented by general formula (1a) include, for example, isophthalaldehyde trimethylolpropane diacetate, isophthalaldehyde trimethylolpropane diacetate, 5-methylisophthalaldehyde trimethylolpropane diacetate, 4-methylisophthalaldehyde trimethylolpropane diacetate, 4-chloroisophthalaldehyde trimethylolpropane diacetate, 5-chloroisophthalaldehyde trimethylolpropane diacetate, 5-bromoisophthalaldehyde trimethylolpropane diacetate, 4-bromoisophthalaldehyde trimethylolpropane diacetate, 2-bromoisophthalaldehyde trimethylolpropane diacetate, 4,6-dimethylisophthalaldehyde trimethylolpropane diacetate, and 2,4-dimethylisophthalaldehyde trimethylolpropane diacetate. Formaldehyde trimethylolpropane diacetate, 2,5-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dibromo-isophthalaldehyde trimethylolpropane diacetate, 2,5-dibromo-isophthalaldehyde trimethylolpropane diacetate, 5-tert-butyl-isophthalaldehyde trimethylolpropane diacetate, 2,4,5,6-tetrafluoro-isophthalaldehyde trimethylolpropane diacetate, 5-(bromomethyl)-isophthalaldehyde trimethylolpropane diacetate, 4-isopropyl-isophthalaldehyde trimethylolpropane diacetate, 4,6-diisopropyl-isophthalaldehyde trimethylolpropane diacetate, 2-bromo-5-tert-butyl- 4-Phenylo-isophthalaldehyde trimethylolpropane diacetate, 5-Phenylo-isophthalaldehyde trimethylolpropane diacetate, 4-Pheny-6-methyl-isophthalaldehyde trimethylolpropane diacetate, 4,5-Diethyl-6-methyl-isophthalaldehyde trimethylolpropane diacetate, 5-Hexyl-isophthalaldehyde trimethylolpropane diacetate, 4-Hexyl-isophthalaldehyde trimethylolpropane diacetate, 5-Butoxy-isophthalaldehyde trimethylolpropane diacetate, 2-Methoxy-isophthalaldehyde trimethylolpropane diacetate, 4-Methoxy-isophthalaldehyde trimethylolpropane diacetate, 5-Methoxy-isophthalaldehyde trimethylolpropane diacetate Hydroxymethyl ethane diacetate, 2-methoxy-4-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methyl-4-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methoxy-5-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4-methyl-6-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4,6-dimethoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2-methoxy-4-ethyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 4,6-dimethyl-2-methoxy-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2,4-dimethoxy-6-methyl-isophthalaldehyde tris(hydroxymethyl)ethane diacetate, 2...4-Dimethyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 4-ethyl-5-methyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 5-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-chloro-isophthalaldehyde trimethylolpropane diacetate, 5-chloro-isophthalaldehyde trimethylolpropane diacetate, 5-bromo-isophthalaldehyde trimethylolpropane diacetate, 4-bromo-isophthalaldehyde trimethylolpropane diacetate, 2-bromo-isophthalaldehyde trimethylolpropane diacetate, 4,6-dimethyl-isophthalaldehyde trimethylolpropane diacetate, 2,4- Dimethyl isophthalaldehyde trimethylolpropane diacetate, 2,5-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dichloro-isophthalaldehyde trimethylolpropane diacetate, 4,6-dibromo-isophthalaldehyde trimethylolpropane diacetate, 2,5-dibromo-isophthalaldehyde trimethylolpropane diacetate, 5-tert-butyl-isophthalaldehyde trimethylolpropane diacetate, 2,4,5,6-tetrafluoro-isophthalaldehyde trimethylolpropane diacetate, acetate, 4-isopropyl-isophthalaldehyde trimethylolpropane diacetate, 4,6-diisopropyl-isophthalaldehyde trimethylolpropane diacetate, 2-bromo-5-tert-butyl-isophthalaldehyde trimethylolpropane diacetate 4-Phenylo-isophthalaldehyde trimethylolpropane diacetal, 5-Phenylo-isophthalaldehyde trimethylolpropane diacetal, 4-Pheny-6-methylisophthalaldehyde trimethylolpropane diacetal, 4,5-Diethyl-6-methylisophthalaldehyde trimethylolpropane diacetal, 5-Hexylisophthalaldehyde trimethylolpropane diacetal, 4-Hexylisophthalaldehyde trimethylolpropane diacetal, 5-Butoxyisophthalaldehyde trimethylolpropane diacetal, 2-Methoxyisophthalaldehyde trimethylolpropane diacetal, 4-Methoxyisophthalaldehyde trimethylolpropane diacetal, 5-Methoxyisophthalaldehyde trimethylolpropane diacetal Diacetal, 2-methoxy-4-methylisophthalaldehyde trimethylolpropane diacetal, 2-methyl-4-methoxyisophthalaldehyde trimethylolpropane diacetal, 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...4-Dimethyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, 4-ethyl-5-methyl-6-methoxy-isophthalaldehyde trimethylolpropane diacetate, etc. Among these, preferred compounds include isophthalaldehyde trimethylolpropane diacetate, isophthalaldehyde trimethylolethane diacetate, 5-methyl-isophthalaldehyde trimethylolethane diacetate, 5-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-isophthalaldehyde trimethylolpropane diacetate, 4-methyl-isophthalaldehyde trimethylolethane diacetate, etc., with particularly preferred compounds including isophthalaldehyde trimethylolpropane diacetate, isophthalaldehyde trimethylolethane diacetate, etc.

[0141] The compound represented by general formula (1b) is shown below.

[0142]

[0143] [In the formula, R] 1 and R 2 Same as above.

[0144] As a preferred R in general formula (1b) 1 The preferred R in general formula (1a) 1 Same. Furthermore, R is the preferred option in general formula (1b). 2 The preferred R in general formula (1a) 2 same.

[0145] The compound represented by general formula (1b) is believed to exist as isomers such as (1b-A), (1b-B), or (1b-C) as described below. These isomers may be individual or in mixtures.

[0146]

[0147] [In the formula, R] 1 and R 2 Same as above.

[0148] When the compound represented by general formula (1b) is a mixture of two or more isomers, gas chromatography (GC) analysis can be performed using the method described in the examples, and the isomer ratio can be determined by the area percentage method. Each isomer typically exhibits its own unique peaks as determined by GC analysis. The proportion of isomers 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 ratio of the percentages of each isomer can be used as the isomer ratio. Alternatively, the cyclic diol compound of the present invention can be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0149] The compound represented by general formula (1b) is considered to exist as isomers such as (1b-A), (1b-B), or (1b-C) as described above. Two or three isomer peaks detected in GC analysis are considered to be isomers (1b-A), (1b-B), or (1b-C). The isomer ratio based on GC analysis can be in the range of isomer (1b-A): isomer (1b-B): isomer (1b-C) = 10–1:10–1:1.

[0150] Specific examples of compounds represented by general formula (1b) include, for example, terephthalaldehyde trimethylolpropane diacetate, terephthalaldehyde trimethylolethane diacetate, 2-methylterephthalaldehyde trimethylolethane diacetate, 3-methylterephthalaldehyde trimethylolethane diacetate, 3-chloroterephthalaldehyde trimethylolethane diacetate, 2-chloroterephthalaldehyde trimethylolethane diacetate, 2-bromoterephthalaldehyde trimethylolethane diacetate, 3-bromoterephthalaldehyde trimethylolethane diacetate, 3,6-dimethylterephthalaldehyde trimethylolethane diacetate, 2,3-dimethylterephthalaldehyde trimethylolethane diacetate, 2,5-dichloroterephthalaldehyde trimethylolethane diacetate, and 3,6-dichloroterephthalaldehyde trimethylolethane diacetate. Diacetal, 3,6-dibromo-terephthalaldehyde trimethylolethane diacetal, 2,5-dibromo-terephthalaldehyde trimethylolethane diacetal, 2-tert-butyl-terephthalaldehyde trimethylolethane diacetal, 2,3,5,6-tetrafluoro-terephthalaldehyde trimethylolethane diacetal, 3-isopropyl-terephthalaldehyde trimethylolethane diacetal, 3,6-diisopropyl-terephthalaldehyde trimethylolethane diacetal, 2-bromo-5-tert-butyl-terephthalaldehyde trimethylolethane diacetal, 3-phenyl-terephthalaldehyde trimethylolethane diacetal, 2-phenyl-terephthalaldehyde trimethylolethane diacetal, 3-phenyl-6-methyl-terephthalaldehyde trimethylolethane diacetal, 3,5-diethyl-6-methyl-terephthalaldehyde trimethylolethane diacetal 2-Hexyl-terephthalaldehyde trimethylolethane diacetate, 3-Hexyl-terephthalaldehyde trimethylolethane diacetate, 2-Butoxy-terephthalaldehyde trimethylolethane diacetate, 3-Methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-3-methyl-terephthalaldehyde trimethylolethane diacetate, 2-Methyl-3-methoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-5-methyl-terephthalaldehyde trimethylolethane diacetate, 3-Methyl-6-methoxy-terephthalaldehyde trimethylolethane diacetate, 3,6-Dimethoxy-terephthalaldehyde trimethylolethane diacetate, 2-Methoxy-3-ethyl-terephthalaldehyde trimethylolethane diacetate, 3 6-Dimethyl-2-methoxy-terephthalaldehyde trimethylolpropane diacetate, 2,3-dimethoxy-6-methyl-terephthalaldehyde trimethylolpropane diacetate, 2,3-dimethyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetate, 3-ethyl-5-methyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetate, 2-methyl-terephthalaldehyde trimethylolpropane diacetate, 3-methyl-terephthalaldehyde trimethylolpropane diacetate, 3-chloro-terephthalaldehyde trimethylolpropane diacetate, 2-chloro-terephthalaldehyde trimethylolpropane diacetate, 2-bromo-terephthalaldehyde trimethylolpropane diacetate, 3-bromo-terephthalaldehyde trimethylolpropane diacetate, 3,6-dimethyl-terephthalaldehyde trimethylolpropane diacetate, 2,3-Dimethylterephthalaldehyde trimethylolpropane diacetate, 2,5-Dichloroterephthalaldehyde trimethylolpropane diacetate, 3,6-Dichloroterephthalaldehyde trimethylolpropane diacetate, 3,6-Dibromoterephthalaldehyde trimethylolpropane diacetate, 2,5-Dibromoterephthalaldehyde trimethylolpropane diacetate, 2-tert-butylterephthalaldehyde trimethylolpropane diacetate, 2,3,5,6-Tetrafluoroterephthalaldehyde trimethylolpropane diacetate, 3-Isopropylterephthalaldehyde trimethylolpropane diacetate Acetal, 3,6-diisopropylterephthalaldehyde trimethylolpropane diacetal, 2-bromo-5-tert-butylterephthalaldehyde trimethylolpropane diacetal, 3-phenylterephthalaldehyde trimethylolpropane diacetal, 2-phenylterephthalaldehyde trimethylolpropane diacetal, 3-phenyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 3,5-diethyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 2-hexylterephthalaldehyde trimethylolpropane diacetal, 3-hexylterephthalaldehyde Trimethylolpropane diacetal, 2-butoxy-terephthalaldehyde trimethylolpropane diacetal, 3-methoxy-terephthalaldehyde trimethylolpropane diacetal, 2-methoxy-terephthalaldehyde trimethylolpropane diacetal, 2-methoxy-3-methyl-terephthalaldehyde trimethylolpropane diacetal, 2-methyl-3-methoxy-terephthalaldehyde trimethylolpropane diacetal, 3-methyl-6-methoxy-terephthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxy-terephthalaldehyde trimethylolpropane diacetal Aldehydes, 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, 2,3-dimethyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, etc. Preferred compounds include terephthalaldehyde trimethylolpropane diacetate, terephthalaldehyde trimethylolpropane diacetate, 2-methylterephthalaldehyde trimethylolpropane diacetate, 2-methylterephthalaldehyde trimethylolpropane diacetate, 3-methylterephthalaldehyde trimethylolpropane diacetate, and 3-methylterephthalaldehyde trimethylolpropane diacetate, with particularly preferred compounds including terephthalaldehyde trimethylolpropane diacetate and terephthalaldehyde trimethylolpropane diacetate.

[0151] The compounds represented by general formula (1c) are shown below.

[0152]

[0153] [In the formula, R] 1 and R 2 Same as above.

[0154] R is the preferred option in general formula (1c) 1 The preferred R in general formula (1a) 1 Same. Furthermore, R is the preferred option in general formula (1c). 2 The preferred R in general formula (1a) 2 same.

[0155] The compound represented by general formula (1c) is believed to exist as isomers such as (1c-A), (1c-B), or (1c-C) as described below. These isomers may be individual or in mixtures.

[0156]

[0157] [In the formula, R] 1 and R 2 Same as above.

[0158] When the compound represented by general formula (1c) is a mixture of two or more isomers, gas chromatography (GC) analysis can be performed using the method described in the examples, and the isomer ratio can be determined by the area percentage method. Each isomer typically exhibits its own unique peaks as determined by GC analysis. The proportion of isomers 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 ratio of the percentages of each isomer can be used as the isomer ratio. Alternatively, the cyclic diol compound of the present invention can be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like before GC analysis.

[0159] The compound represented by general formula (1c) is considered to exist as isomers such as (1c-A), (1c-B), or (1c-C) as described above. If two or three isomer peaks are detected in the GC analysis, these are considered to be isomers (1c-A), (1c-B), or (1c-C). The isomer ratio based on GC analysis can be in the range of isomer (1c-A): isomer (1c-B): isomer (1c-C) = 10–1:10–1:1.

[0160] Specific examples of compounds represented by general formula (1c) include, for example, phthalaldehyde trimethylolpropane diacetate, phthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, 3-chlorophthalaldehyde trimethylolpropane diacetate, 3-bromophthalaldehyde trimethylolpropane diacetate, 3,6-dimethylphthalaldehyde trimethylolpropane diacetate, 3,4-dimethylphthalaldehyde trimethylolpropane diacetate, 3,5-dimethylphthalaldehyde trimethylolpropane diacetate, 4,5-dimethylphthalaldehyde trimethylolpropane diacetate, and 3,6-dichlorophthalaldehyde trimethylolpropane diacetate. Methyl ethane diacetate, 3,6-dibromophthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-diethyl-4-methylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-hexylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-butoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxy-6-methylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methyl-6-methoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-dimethoxyphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3-methoxy-6-ethylphthalaldehyde tris(hydroxymethyl)ethane diacetate, 3,6-dimethyl-4-methoxyphthalaldehyde Formaldehyde trimethylolpropane diacetate, 3,6-dimethoxy-4-methylphthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, 3-chlorophthalaldehyde trimethylolpropane diacetate, 3-bromophthalaldehyde trimethylolpropane diacetate, 3,6-dimethylphthalaldehyde trimethylolpropane diacetate, 3,4-dimethylphthalaldehyde trimethylolpropane diacetate, 3,5-dimethylphthalaldehyde trimethylolpropane diacetate, 4,5-dimethylphthalaldehyde trimethylolpropane diacetate, 3,6-dichlorophthalaldehyde trimethylolpropane diacetate, 3,6-dibromophthalaldehyde trimethylolpropane diacetate, 3,6-dibromophthalaldehyde trimethylolpropane diacetate Phthalate trimethylolpropane diacetate, 3,6-diethyl-4-methylphthalaldehyde trimethylolpropane diacetate, 3-hexylphthalaldehyde trimethylolpropane diacetate, 3-butoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxy-6-methylphthalaldehyde trimethylolpropane diacetate, 3-methyl-6-methoxyphthalaldehyde trimethylolpropane diacetate, 3,6-dimethoxyphthalaldehyde trimethylolpropane diacetate, 3-methoxy-6-ethylphthalaldehyde trimethylolpropane diacetate, 3,6-dimethyl-4-methoxyphthalaldehyde trimethylolpropane diacetate, 3,6-Dimethoxy-4-methylphthalaldehyde trimethylolpropane diacetate, wherein preferred compounds include phthalaldehyde trimethylolpropane diacetate, phthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 3-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, 4-methylphthalaldehyde trimethylolpropane diacetate, etc., and particularly preferred compounds include phthalaldehyde trimethylolpropane diacetate, phthalaldehyde trimethylolpropane diacetate, etc.

[0161] 2. Manufacturing method of resin modifier

[0162] The method of manufacturing the compound shown in general formula (1) is not particularly limited. For example, it can be manufactured by reacting the compound shown in general formula (3) with the compound shown in general formula (4) as shown in <Reaction Formula 1> below (acetalization reaction).

[0163] <Reaction Formula 1>

[0164]

[0165] [In the formula, R] 1 And ring A is the same as described above.

[0166] Specifically, the compound represented by general formula (1) can be produced by reacting the compound represented by general formula (3) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction).

[0167] The reaction is usually carried out in a solvent (e.g., toluene). The reaction can be carried out while the solvent is heated under reflux and the generated water is removed by azeotropic reaction with the solvent. As an acid catalyst, there is no particular limitation as long as it has a catalytic effect, and any known acid catalyst can be used. Examples 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, and trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, silica-alumina, and heteropoly acids (e.g., phosphotungstic acid, phosphomolybdic acid, etc.); and various other Lewis acids. The amount of the compound shown in general formula (4) used is usually about 0.5 to 3 moles relative to 1 mole of the compound shown in general formula (3), preferably about 0.8 to 2 moles.

[0168] The compounds contained in the compound shown in general formula (1), the compound shown in general formula (1a), the compound shown in general formula (1b) and the compound shown in general formula (1c) can also be prepared in the same manner as <Reaction Formula 1>.

[0169] The compound represented by general formula (1a) can be produced as shown in <Reaction Formula 2> below by reacting the compound represented by general formula (3a) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction).

[0170] <Reaction 2>

[0171]

[0172] [In the formula, R] 1 and R 2 Same as above.

[0173] The compound represented by general formula (1b) can be prepared by reacting the compound represented by general formula (3b) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction), as shown in <Reaction Formula 3> below.

[0174] <Reaction Formula 3>

[0175]

[0176] [In the formula, R] 1 and R 2 Same as above.

[0177] The compound represented by general formula (1c) can be prepared by reacting the compound represented by general formula (3c) with the compound represented by general formula (4) in the presence of an acidic catalyst (acetalization reaction), as shown in <Reaction Formula 4> below.

[0178] <Reaction Formula 4>

[0179]

[0180] [In the formula, R] 1 and R 2 Same as above.

[0181] 3. Manufacturing of resins using resin modifiers

[0182] The compound shown in general formula (1) (cyclic diol compound) can be used as a raw material monomer for manufacturing resin, and polymerized alone or in combination with other monomers to produce a resin containing repeating units (structural units) shown in general formula (2). Examples of resins include those having polyester bonds, polycarbonate bonds, polyurethane bonds, etc., within the molecule. Specifically, examples include polyester resin, polyester carbonate resin, polycarbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin, polyester polyol resin, etc. Polyester resin, polyester carbonate resin, polycarbonate resin, and polyurethane resin are preferred, and polyester carbonate resin and polycarbonate resin are even more preferred.

[0183] When the resin is polyester carbonate resin or polycarbonate resin, it preferably contains repeating units (structural units) as shown in the following general formula (2).

[0184]

[0185] [In the formula, R] 1 And ring A is the same as described above.

[0186] In general formula (2), R 1 The specific examples and preferred examples of ring A are the same as those described in the aforementioned general formula (1) for R. 1 The specific examples and preferred examples of ring A are the same.

[0187] The compounds contained in the compound shown in general formula (1), as well as those shown in general formula (1a), general formula (1b) and general formula (1c), can also be polymerized alone or in combination with other monomers to produce polyester carbonate resins or polycarbonate resins containing repeating units (structural units) shown in general formula (2a), general formula (2b) or general formula (2c) respectively.

[0188]

[0189] [In the formula, R] 1 and R 2 Same as above.

[0190]

[0191] [In the formula, R] 1 and R 2 Same as above.

[0192]

[0193] [In the formula, R] 1 and R 2 Same as above.

[0194] In the case of a polycarbonate resin containing repeating units (structural units) as shown in general formula (2), it can be manufactured by reacting a raw material monomer containing a compound as shown in general formula (1) with a carbonyl precursor compound (polymerization).

[0195] As a raw material monomer for polycarbonate resin, the compound shown in general formula (1) can be used alone. The resulting polycarbonate resin is a homopolymer obtained by polymerizing only the compound shown in general formula (1) with a carbonyl precursor compound, containing only the structural unit shown in general formula (2). As such a homopolymer, it is preferable to be a homopolymer having the structural unit shown in general formula (2a) or the structural unit shown in general formula (2c).

[0196] In addition to the compound shown in general formula (1), the raw material monomers of polycarbonate resin may also contain dihydroxy compounds that are commonly used as structural units of polycarbonate resin. Examples of such dihydroxy compounds include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.

[0197] That is, the polycarbonate resin can be a copolymer containing structural units from general dihydroxy compounds in addition to the structural units from the compound represented by general formula (2) represented by general formula (1). The copolymer having multiple structural units can be any of block copolymers or random copolymers.

[0198] As aliphatic dihydroxy compounds, various aliphatic dihydroxy compounds can be listed, particularly 1,4-cyclohexanediethanol, tricyclodecanediethanol, 1,3-adamantanediethanol, 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-propanediol, 1,4-butanediol, 1,6-hexanediol, etc.

[0199] As aromatic dihydroxy compounds, various aromatic dihydroxy compounds can be listed, 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'-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl) ethers, bis(4-hydroxyphenyl) sulfides, bis(4-hydroxyphenyl) sulfoxides, as well as bis(4-hydroxyphenyl) ketones, bisphenoxyethanol fluorene, etc. Additionally, hydroquinone, resorcinol, and catechol can also be listed.

[0200] The proportion of the compound represented by general formula (1) in the raw material monomers used is not particularly limited, but in the total amount of monomers, it 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%. That is, in the polycarbonate resin, the proportion of the structural unit represented by general formula (2) from the compound represented by general formula (1) is not particularly limited, but in all structural units, it 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%.

[0201] Examples of carbonyl precursor compounds include phosgene, triphosgene, and diphenyl carbonate.

[0202] In addition to the compound shown in general formula (1), the raw material monomers of polyester carbonate resin may also contain dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic acid anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc., which are commonly used as structural units of polyester carbonate resins. Examples of such dihydroxy compounds include, for example, the aforementioned aliphatic dihydroxy compounds and aromatic dihydroxy compounds. Preferably, the raw material monomers also contain structural units, for example, from at least one monomer selected from the group consisting of the following monomers.

[0203]

[0204] [In the formula, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group; 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.]

[0205] That is, in addition to containing structural units of general formula (2) derived from compounds of general formula (1), polyester carbonate resins may also contain structural units derived from general dihydroxy compounds, dicarboxylic acid compounds, dicarboxylic acid anhydride compounds, hydroxycarboxylic acid compounds, hydroxycarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc. Copolymers having multiple structural units can be either block copolymers or random copolymers.

[0206] The polycarbonate resin or polyester carbonate resin containing the structural unit shown in general formula (2) has a number-average molecular weight (Mn) of about 4,000 to about 100,000, preferably about 10,000 to about 50,000, a weight-average molecular weight (Mw) of about 5,000 to about 100,000, preferably about 6,000 to about 80,000, and a polydispersity index (Mw / Mn) of about 1 to about 5, preferably about 1.5 to about 4.5. Furthermore, the glass transition temperature (Tg) is about 100°C to about 200°C, preferably about 120°C to about 160°C.

[0207] The refractive index (n) of polycarbonate resin or polyester carbonate resin containing the structural unit shown in general formula (2) D The refractive index is relatively large, typically 1.500 to 1.750, preferably 1.520 to 1.650. The refractive index is a value measured by the method described in the examples.

[0208] The Abbe number (ν) of birefringence of polycarbonate resin or polyester carbonate resin containing the structural unit shown in general formula (2) d The value is typically 20.0 to 55.0, preferably 24.0 to 45.0. The Abbe number is a value measured by the method described in the examples.

[0209] 4. Applications of the modified resin

[0210] The compound represented by general formula (1) is used as a homopolymer monomer or as a copolymer monomer for polymerization, thereby modifying the properties of the resin. For example, by adjusting the amount of the compound represented by general formula (1) added and copolymerizing it with other monomers, the refractive index, birefringence, and other properties of the resin can be adjusted.

[0211] Therefore, the resin obtained using the resin modifier of the present invention is suitable for use, for example, in optical components. Optical components include, but are not limited to, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, bases, filters, hard coatings, etc. The resin of the present invention has high fluidity and can be formed by casting, making it particularly suitable for manufacturing thin optical components. In a preferred embodiment of the present invention, examples of optical components manufactured using the resin of the present invention include optical lenses, optical films, and optical sheets.

[0212] The resin of this invention is suitable for use in optical lenses. Optical lenses made using the resin of this invention (especially polycarbonate resin) are extremely useful in fields where expensive high-refractive-index glass lenses were previously used, due to their high refractive index and excellent heat resistance.

[0213] Furthermore, the refractive index of the resin of the present invention can be adjusted over a wide range according to the design of various optical lenses by adjusting the content of structural units from the compound represented by general formula (1).

[0214] The resin of the present invention is suitable for use in optical films. Optical films made using the resin of the present invention (especially polycarbonate resin) are suitable for use in liquid crystal substrate films, optical memory cards, etc., due to their excellent transparency and heat resistance.

[0215] The resin of the present invention can make birefringence infinitely close to zero by adjusting the content of structural units from the compound represented by general formula (1).

[0216] Generally, birefringence observed in resins used for polymerized optical components is classified into oriented birefringence, stress birefringence, and morphological birefringence. Morphological birefringence is the birefringence observed when fine fibrous materials within the resin are arranged; therefore, the optical properties of the resin used for optical components are usually negligible. Oriented birefringence is based on molecular orientation, while stress birefringence arises from residual stress during molding.

[0217] For resins used in optical components, high birefringence leads to greater optical strain, which can cause problems such as exudation and blurring when used in optical lenses. Therefore, to achieve clearer visual performance, it is necessary to reduce birefringence.

[0218] Resins commonly used for optical components include various resins, especially polyester resin, polyester carbonate resin, and polycarbonate resin. Polyester carbonate resin or polycarbonate resin, in particular, has excellent transparency, impact resistance, heat resistance, and dimensional stability.

[0219] More specifically, resins (especially polycarbonate resins) obtained by homopolymerization or copolymerization using compounds of general formula (1) exhibit a property where the birefringence intensity increases in the order of general formulas (1c), (1a), and (1b). These compounds are excellent at adjusting the birefringence intensity of resins. By copolymerizing structural units from compounds of general formula (1) with structural units from other dihydroxy compounds, resins with birefringence approaching zero can be manufactured. This resin is suitable for applications requiring birefringence approaching zero, particularly for optical components such as optical lenses, optical films, and optical sheets. There are no particular limitations on applicable optical components; examples include lenses for smartphone cameras, lenses for automotive cameras, lenses for VR (virtual reality) or MR (mixed reality) goggles, and lenses for crime prevention cameras.

[0220] In this specification, the expressions “comprising” or “containing” include the meanings of “must be composed of” and “composed of only”.

[0221] Example

[0222] The following examples illustrate the present invention in detail, but the invention is not limited to these examples. It should be noted that in these examples, various determinations of the cyclic diol compounds were performed according to the following methods. Additionally, reagents were used for compounds not specifically mentioned.

[0223] <Using Compounds>

[0224] • Isophthalaldehyde: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0225] • Terephthalaldehyde: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0226] • Phthalate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0227] p-Toluenesulfonic acid monohydrate: manufactured by Nakaraite Co., Ltd.

[0228] • Trimethylolethane and trimethylolpropane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0229] • Bisphenoxyethanol fluorene (BPEF): Manufactured by Tokyo Chemical Industry Co., Ltd.

[0230] • Diphenyl carbonate: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0231] <Analysis using gas chromatography (GC)>

[0232] Gas chromatography (GC) analysis was performed according to the following conditions and methods, and the purity of the cyclic diol compound was determined by the area percentage method.

[0233] (Sample preparation)

[0234] A methanol solution of the cyclic diol compound was prepared by adding 50 ml of methanol to 0.5 g of the cyclic diol compound and shaking the mixture at room temperature. This solution was then used as an analytical sample.

[0235] [Measurement Conditions]

[0236] Equipment: Shimadzu Corporation GC-2020

[0237] Column: DB-1 manufactured by Agilent Technologies, Inc. 30m × 0.25mm × 0.25μm

[0238] Column temperature: 80℃ (holding time 5 minutes) - heating rate 10℃ / minute - 320℃ (holding time 5 minutes)

[0239] Injection temperature / detector temperature: 300℃ / 325℃

[0240] Flow split ratio: 30

[0241] Column flow rate: 1.17 ml / min

[0242] Purging flow rate: 10.0 ml / min

[0243] Detector: FID

[0244] Carrier gas: Helium

[0245] Gas linear velocity: 30 cm / s

[0246] Injection volume: 1 μl

[0247] <Melting Point>

[0248] The melting point of the cyclic diol compound was determined using a differential calorimeter (DSC6220) manufactured by Estiay Nanotecello Corporation. A 10.7 mg sample was placed in an aluminum dish manufactured by this company and sealed. The temperature was increased from 30 °C to 200 °C at a rate of 10 °C / min under a nitrogen flow of 50 ml / min, and the endothermic peak was observed. The temperature indicated by the peak was taken as the melting point.

[0249] <Infrared Absorption Spectrum (IR Spectrum)>

[0250] The IR spectra of the cyclic diol compounds were obtained using an infrared spectrophotometer (Spectrum 400 manufactured by PerkinElmer Japan Co., Ltd.) via the ATR (attenuated total reflectance) method.

[0251] <Proton nuclear magnetic resonance spectrum ( 1 H-NMR)

[0252] Regarding cyclic diol compounds 1 H-NMR, after dissolving in a deuterated solvent (deuterated chloroform or deuterated methanol), was performed using a nuclear magnetic resonance apparatus (DRX-500 manufactured by Bruker). 1 The measurements were performed using H-NMR (500MHz).

[0253] It should be noted that, 1 In the solvents used for H-NMR determination, water peaks are sometimes observed. The water peak from deuterated chloroform is located around 1.56 ppm, and the water peak from deuterated methanol is located around 4.87 ppm.

[0254] <Glass transition temperature>

[0255] The glass transition temperature of the obtained polycarbonate resin was determined using a differential calorimeter (DSC6220) manufactured by Estiay Nanotecello Corporation. A 6.7 mg sample was placed in an aluminum dish manufactured by Estiay and sealed. Under a nitrogen flow of 50 ml / min, the temperature was increased from 30°C to 220°C at a heating rate of 10°C / min, cooled from 220°C to 30°C at a cooling rate of 10°C / min, and then increased from 30°C to 220°C at a heating rate of 10°C / min. The inflection point in the second run was taken as the glass transition temperature.

[0256] Number-average molecular weight, weight-average molecular weight, and polydispersity index

[0257] Dissolve approximately 30 mg of polycarbonate resin in 8 ml of tetrahydrofuran to prepare a sample solution for molecular weight determination. For the number-average molecular weight (Mn) and weight-average molecular weight (Mw), use gel permeation chromatography (GPC) under the following determination conditions to determine the converted number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity index (Mw / Mn) of polystyrene.

[0258] (Measurement conditions)

[0259] Device: Pump (Shimadzu Corporation LC-20AD type)

[0260] Automatic sampler (Shimadzu Corporation SIL-20A HT type)

[0261] Detector RI (RID-10A type, manufactured by Shimadzu Corporation)

[0262] Column thermostat (model CTO-20A manufactured by Shimadzu Corporation)

[0263] Column: Shodex LF-802, 2 pieces (manufactured by Showa Denko Co., Ltd.)

[0264] Eluent: Tetrahydrofuran (THF) manufactured by Nakaraite Co., Ltd., containing approximately 0.025% BHT.

[0265] Column temperature: 40℃

[0266] Flow rate: 1.0 mL / min

[0267] Injection volume: 100 μl

[0268] Analytical method: Molecular weight conversion using PS

[0269] Standard polymer used: Shodex Standard SM-105

[0270] <Refractive Index>

[0271] For the polycarbonate resins obtained in the manufacturing examples described below, 0.8 g of 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, Ltd., followed by heating at 20 MPa for 30 seconds, and then heating at 10 MPa for 1 minute and 30 seconds. After cooling for 3 minutes, a polycarbonate film with a thickness of 0.1 mm was obtained.

[0272] A rectangular test piece with a length of 40 mm and a width of 8 mm was cut from the 0.1 mm thick film as the test sample. Using an interference filter with a wavelength of 589 nm (D-rays), the refractive index n was determined using a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd., according to the method of JIS-K-7142. D In the determination, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the intermediate solution.

[0273] <Total transmittance>

[0274] A 0.1 mm thick film prepared using the aforementioned <refractive index> method was used as the test sample. The total transmittance was measured using a HazeMater NDH7000SPII laser manufactured by Nippon Denshoku according to the JIS-K-7136 method. Measurements were performed on three films, and the average of the measured values ​​obtained from these measurements was taken as the final value.

[0275] <Abbe Numbers>

[0276] A rectangular test piece with a length of 40 mm and a width of 8 mm was cut from a 0.1 mm thick film prepared using the aforementioned <refractive index> method, and used as the test sample. Using interference filters with wavelengths of 656 nm (C-rays), 589 nm (D-rays), and 486 nm (F-rays), the refractive index n at each wavelength was measured 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 measurements and the following formula. d .

[0277] vD=(nD-1) / (nF-nC)

[0278] In the determination, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the intermediate solution.

[0279] <Birefringence>

[0280] For the samples, a tensile fixture was set in a solid viscoelasticity measuring apparatus (UBM, S1000-DVE3) for heated uniaxial stretching. After stretching was stopped, the thermostatic bath was opened and cooled by a blower. For the stretched film, a Luminers Ace LA-100USW manufactured by HAYASHI-REPIC Co., Ltd. was used as the light source, and a phase difference measuring apparatus KOBRA-WPR manufactured by Oji Measurement & Control Co., Ltd. was used to measure the phase difference at wavelengths of 449.9 nm, 498.0 nm, 548.0 nm, 588.8 nm, 628.8 nm, and 751.0 nm. The birefringence Δn was calculated from the phase difference at wavelength 588.8 nm and the film thickness using the following formula. It should be noted that when the slow axis is aligned with the stretching direction, Δn is represented by a positive value; when the slow axis is aligned with the perpendicular direction, Δn is represented by a negative value.

[0281] Birefringence Δn = (Phase difference at wavelength 588.8 nm [nm]) / (Film thickness [mm] × 10 6 )

[0282] <Synthesis of Cyclic Diol Compounds>

[0283] [Example 1]

[0284] Add 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 to a 500 ml four-necked Dean-Stark flask equipped with a stirrer, thermometer, and condenser. Then heat the flask and stir under reflux to remove the water generated for about 6 hours.

[0285] The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 59 ml of toluene under reduced pressure. 100 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off and washed twice with 50 ml of ion-exchanged water, then twice with 100 ml of 60°C warm water, and finally twice with 50 ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 80°C to obtain 26.7 g (0.08 mol) of isophthalaldehyde trimethylolethane diacetate (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.

[0286] For the obtained m-phthalaldehyde trihydroxymethyl ethane diacetate, the IR spectrum was determined and 1 H-NMR spectra. The results are shown in... Figure 1 and Figure 2 .Depend on Figure 1 The following characteristic peaks and Figure 2 It was confirmed to be isophthalaldehyde trihydroxymethyl ethane diacetal.

[0287] IR (cm) -1 ): 653, 690, 714, 803, 891, 962, 982, 1007, 1024, 1043, 1100, 1164, 1378, 2866, 2955, 3349

[0288] [Example 2]

[0289] Add 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 to a 500 ml four-necked Dean-Stark flask equipped with a stirrer, thermometer, and condenser. Then heat the flask and stir under reflux to remove the generated water for about 8 hours.

[0290] The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 60 ml of toluene under reduced pressure. 150 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered out and washed twice with 50 ml of ion-exchanged water, then twice with 100 ml of 60°C warm water. Finally, the crystals were washed twice with 50 ml 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). 60 g of isopropanol was added to the obtained crystals and heated to dissolve them. After distilling off 40 g of isopropanol, 100 ml of water was added. The precipitated crystals were filtered out and washed twice with 50 ml of ion-exchanged water. The wet crystals were 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 crystal is 95.5℃.

[0291] For the obtained m-phthalaldehyde trimethylolpropane diacetal, the IR spectrum was determined and 1 H-NMR spectra. The results are shown in... Figure 3 and Figure 4 .Depend on Figure 3 The following characteristic peaks and Figure 4 It was confirmed to be isophthalaldehyde trimethylolpropane diacetal.

[0292] IR (cm) -1 ): 712, 803, 933, 971, 1030, 1101, 1165, 1377, 2859, 2962, 3374

[0293] [Example 3]

[0294] Add 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 to a 500 ml four-necked flask equipped with a stirrer, thermometer, and condenser. Then heat the flask and stir under reflux to remove the generated water for about 6 hours.

[0295] The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 50 ml of toluene under reduced pressure. 100 g of deionized water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off and washed twice with 50 ml of deionized water, followed by two washes with 50 ml of 60°C warm water. The wet crystals were dried under reduced pressure at 100°C to obtain 30.4 g (0.09 mol) 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.

[0296] For the obtained terephthalaldehyde trihydroxymethyl ethane diacetate, the IR spectrum was determined and 1 H-NMR spectra. The results are shown in... Figure 5 and Figure 6 .Depend on Figure 5 The following characteristic peaks and Figure 6 It was confirmed to be terephthalaldehyde trihydroxymethyl ethane diacetal.

[0297] IR (cm) -1 ): 656, 778, 804, 918, 964, 977, 993, 1016, 1042, 1094, 1374, 2844, 2933, 2959, 3413

[0298] [Example 4]

[0299] Add 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 to a 500 ml four-necked flask equipped with a stirrer, thermometer, and condenser. Then heat the flask and stir under reflux to remove the water generated for about 10 hours.

[0300] The reaction mixture was brought to room temperature, neutralized with 1 g of triethylamine, and then distilled off 50 ml of toluene under reduced pressure. 150 g of ion-exchanged water was added, and the mixture was cooled with ice water. The resulting crystals were filtered off and washed twice with 50 ml of ion-exchanged water, then twice with 50 ml 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). 140 g of isopropanol was added to the obtained crystals and heated to dissolve them. After distilling off the isopropanol, the precipitated crystals were filtered off and washed twice with 50 ml of ion-exchanged water. The wet crystals were dried under reduced pressure at 100°C to obtain 30.0 g (0.08 mol) of terephthalaldehyde trimethylolpropane diacetal (hereinafter referred to as compound 4) with a purity of 97.0% (GC area percentage). The melting point of the crystals was 187.2°C.

[0301] For the obtained terephthalaldehyde trimethylolpropane diacetal, the IR spectrum was determined and 1 H-NMR spectra. The results are shown in... Figure 7 and Figure 8 .Depend on Figure 7 The following characteristic peaks and Figure 8 It was confirmed to be terephthalaldehyde trimethylolpropane diacetal.

[0302] IR (cm) -1 ): 801, 971, 1000, 1018, 1099, 1379, 2855, 2928, 2967, 3355

[0303] [Example 5]

[0304] Add 40.2 g (0.3 mol) of o-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 to a 1000 ml four-necked flask equipped with a stirrer, thermometer, and condenser. Then heat the flask and stir under reflux conditions to remove the water generated for about 4 hours.

[0305] After distilling off 170 ml of xylene under reduced pressure, the reaction mixture was brought to room temperature, neutralized with 25 ml of saturated sodium bicarbonate, and then 400 g of deionized water was added. 100 ml of ethyl acetate was added, and the mixture was separated into an organic layer and an aqueous layer using a separatory funnel. 100 ml of ethyl acetate was added to the aqueous layer, and the organic and aqueous layers were separated. This operation was repeated twice. The resulting organic layer was concentrated using a rotary evaporator. The obtained crystals were 90.2 g (0.27 mol) of o-phthalaldehyde trimethylolethane diacetate (hereinafter referred to as compound 5) with a purity of 99.2% (GC area percentage).

[0306] For the obtained o-phthalaldehyde trihydroxymethyl ethane diacetate, the IR spectrum was determined and 1 H-NMR spectra. The results are shown in... Figure 9 and Figure 10 .Depend on Figure 9 The following characteristic peaks and Figure 10 It was confirmed to be phthalaldehyde trihydroxymethyl ethane diacetal.

[0307] IR (cm) -1 ): 663, 698, 760, 920, 948, 969, 1003, 1021, 1042, 1082, 1099, 1203, 1386, 1455, 2850, 2955, 3414

[0308] <Resin Manufacturing and Physical Property Evaluation>

[0309] [Manufacturing Example 1] (Manufacturing of Polycarbonate Resin 1)

[0310] Compound 1 obtained in Example 1, 9.5 g (0.03 mol), bisphenoxyethanol fluorene, 49.2 g (0.11 mol), diphenyl carbonate, 30.9 g (0.15 mol), and 2.5 × 10⁻⁶ ppm were added. -2 283.29 μL (70.8 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L. - 7 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0311] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0312] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 45g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 1 was pulverized, and the glass transition temperature was measured, which was 148℃. The number-average molecular weight Mn was 20240, the weight-average molecular weight Mw was 34640, and the polydispersity index Mw / Mn was 1.71.

[0313] The refractive index is 1.619. At a wavelength of 588.8 nm, the birefringence is +0.006 × 10⁻⁶. -2 The Abbe number is 25.6. The total transmittance is 90%. The results are shown in Table 1.

[0314] [Manufacturing Example 2] (Manufacturing of Polycarbonate Resin 2)

[0315] Compound 1 obtained in Example 1, 7.6 g (0.02 mol), 23.0 g (0.05 mol) of bisphenoxyethanol fluorene, 16.5 g (0.08 mol) of diphenyl carbonate, and 2.5 × 10⁻⁶ ppm were added. -2 30.2 μL (76.1 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L -8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0316] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0317] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 28g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 2 was pulverized, and its glass transition temperature was measured, which was 143℃. The number-average molecular weight Mn was 27800, the weight-average molecular weight Mw was 56000, and the polydispersity index Mw / Mn was 2.00.

[0318] The refractive index is 1.610. At a wavelength of 588.8 nm, the birefringence is +0.033 × 10⁻⁶. -2 The Abbe number is 26.8. The total transmittance is 90%. The results are shown in Table 1.

[0319] [Manufacturing Example 3] (Manufacturing of Polycarbonate Resin 3)

[0320] Compound 1 obtained in Example 1, 23.0 g (0.07 mol), bisphenoxyethanol fluorene, 29.8 g (0.07 mol), diphenyl carbonate, 29.9 g (0.14 mol), and 2.5 × 10⁻⁶ ppm were added. -2 54.9 μL (137.2 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L. - 8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0321] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0322] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 35g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 3 was pulverized, and the glass transition temperature was measured, which was 145℃. The number-average molecular weight Mn was 26300, the weight-average molecular weight Mw was 53630, and the polydispersity index Mw / Mn was 2.04.

[0323] The refractive index is 1.588. At a wavelength of 588.8 nm, the birefringence is +0.062 × 10⁻⁶. -2 The Abbe number is 28.5. The total transmittance is 90%. The results are shown in Table 1.

[0324] [Manufacturing Example 4] (Manufacturing of Polycarbonate Resin 4)

[0325] Compound 1 obtained in Example 1, 15.4 g (0.05 mol), diphenyl carbonate, 10.0 g (0.05 mol), and 2.5 × 10⁻⁶ mol were added.-2 18.4 μL (46.0 × 10⁻⁶ mol / L sodium bicarbonate aqueous solution) -8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0326] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0327] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 12g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 4") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 4 was pulverized, and the glass transition temperature was measured, which was 127℃. The number-average molecular weight Mn was 19920, the weight-average molecular weight Mw was 51900, and the polydispersity index Mw / Mn was 2.61.

[0328] The refractive index is 1.525. At a wavelength of 588.8 nm, the birefringence is +0.165 × 10⁻⁶. -2 The Abbe number is 43.0. The total transmittance is 92%. The results are shown in Table 1.

[0329] [Manufacturing Example 5] (Manufacturing of polycarbonate resin 5)

[0330] Compound 2 obtained in Example 2, 10.4 g (0.03 mol), 49.9 g (0.11 mol) of bisphenoxyethanol fluorene, 31.3 g (0.15 mol) of diphenyl carbonate, and 2.5 × 10⁻⁶ mol of sodium carbonate were added. -2 286.9 μL (717.0 × 10⁻⁶) mol / L sodium bicarbonate aqueous solution - 8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0331] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0332] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 45g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 5 was pulverized, and the glass transition temperature was measured, which was 132℃. The number-average molecular weight Mn was 4350, the weight-average molecular weight Mw was 7850, and the polydispersity index Mw / Mn was 1.80.

[0333] The refractive index is 1.620. At a wavelength of 588.8 nm, the birefringence is +0.008 × 10⁻⁶. -2 The Abbe number is 25.7. The total transmittance is 90%. The results are shown in Table 1.

[0334] [Manufacturing Example 6] (Manufacturing of Polycarbonate Resin 6)

[0335] Compound 3 obtained in Example 3, 9.5 g (0.03 mol), 49.2 g (0.11 mol) of bisphenoxyethanol fluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 2.5 × 10⁻⁶ ppm were added. -2 283.6 μL (70.9 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L. -7 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0336] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0337] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 45g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 6") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 6 was pulverized, and its glass transition temperature was measured to be 148℃. The number-average molecular weight Mn was 18270, the weight-average molecular weight Mw was 33430, and the polydispersity index Mw / Mn was 1.83.

[0338] The refractive index is 1.620. At a wavelength of 588.8 nm, the birefringence is +0.013 × 10⁻⁶. -2 The Abbe number is 25.7. The total transmittance is 90%. The results are shown in Table 1.

[0339] [Manufacturing Example 7] (Manufacturing of Polycarbonate Resin 7)

[0340] 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 × 10⁻⁶ ppm were added. -2 55.0 μL (137.5 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L -8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0341] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0342] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 45g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 7") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 7 was pulverized, and the glass transition temperature was measured, which was 152.2℃. The number-average molecular weight Mn was 28570, the weight-average molecular weight Mw was 73910, and the polydispersity index Mw / Mn was 2.59.

[0343] The refractive index is 1.610. At a wavelength of 588.8 nm, the birefringence is +0.052 × 10⁻⁶. -2 The Abbe number is 27.5. The total transmittance is 90%. The results are shown in Table 1.

[0344] [Manufacturing Example 8] (Manufacturing of polycarbonate resin 8)

[0345] Compound 4 obtained in Example 4, 10.6 g (0.02 mol), 49.2 g (0.11 mol) of bisphenoxyethanol fluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 2.5 × 10⁻⁶ mol of bisphenoxyethanol fluorene were added. -2 283.5 μL (70.9 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L. -7 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0346] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0347] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 45g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 8") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 8 was pulverized, and its glass transition temperature was measured, which was 140℃. The number-average molecular weight Mn was 11790, the weight-average molecular weight Mw was 50470, and the polydispersity index Mw / Mn was 4.28.

[0348] The refractive index is 1.622. At a wavelength of 588.8 nm, the birefringence is +0.014 × 10⁻⁶. -2 The Abbe number is 25.7. The total transmittance is 90%. The results are shown in Table 1.

[0349] [Manufacturing Example 9] (Manufacturing of polycarbonate resin 9)

[0350] Compound 5 obtained in Example 5 was prepared in the following proportions: 5.8 g (0.02 mol) of compound 5, 30.3 g (0.07 mol) of bisphenoxyethanolfluorene, 19.1 g (0.09 mol) of diphenyl carbonate, and 2.5 × 10⁻⁶ mol of... -2 34.9 μL (87.3 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L. -8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0351] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0352] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 25g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin 9") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin 9 was pulverized, and the glass transition temperature was measured, which was 146.1℃. The number-average molecular weight Mn was 15400, the weight-average molecular weight Mw was 39800, and the polydispersity index Mw / Mn was 2.58.

[0353] The physical properties of the obtained polycarbonate film were determined. The refractive index is 1.619. The birefringence at a wavelength of 588.8 nm is -0.004 × 10⁻⁶. -2 The Abbe number is 26.0. The total transmittance is 89%. The results are shown in Table 1.

[0354] [Comparative Manufacturing Example 1] (Manufacturing of Polycarbonate Resin A)

[0355] 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 (137.5 × 10⁻⁶) of sodium bicarbonate aqueous solution with a concentration of mol / L -8 mol) was added to a 300 mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere and heated to 200 °C.

[0356] After the matrix is ​​dissolved, the temperature is gradually increased to 240°C over 80 minutes, and the pressure is gradually reduced to 150 mmHg.

[0357] The pressure was further reduced to vacuum in stages over 40 minutes, maintained for 20 minutes, and then 55g of the generated polycarbonate resin (hereinafter referred to as "polycarbonate resin A") was taken out. It should be noted that the associated phenol was distilled off during the reaction. The taken-out polycarbonate resin A was pulverized, and the glass transition temperature was measured, which was 147℃. The number-average molecular weight Mn was 21940, the weight-average molecular weight Mw was 41680, and the polydispersity index Mw / Mn was 1.90.

[0358] The refractive index is 1.638. At a wavelength of 588.8 nm, the birefringence is -0.023 × 10⁻⁶. -2 The Abbe number is 23.5. The total transmittance is 90%. The results are shown in Table 1.

[0359]

[0360] As can be seen from Manufacturing Examples 1-9 in Table 1, the polycarbonate resins obtained using compounds 1-5 have high refractive indices and high Abbe numbers. Furthermore, it can be seen that the birefringence intensity of the resin increases in the order of compound 5, compound 1, and compound 3 (in the order of ortho, meta, and para positions of the two acetal groups on the benzene ring). This can be readily understood by comparing the birefringence of the resins obtained in Manufacturing Examples 1, 6, and 9 when the copolymerization ratio (BPEF: cyclic diol compound) is 80:20. As a result, the compounds of the present invention can be appropriately selected and combined according to the desired birefringence intensity of the resin.

[0361] Comparison of manufacturing example 1 with manufacturing examples 1-4, and comparison of manufacturing example 1 with manufacturing examples 6 and 7, shows that by changing the copolymerization ratio of compound 1 or compound 3 as raw material monomers, the refractive index, birefringence, and Abbe number of the obtained polycarbonate resin can be adjusted.

[0362] Compounds 1 and 2 (included in the compound shown in general formula (1a)) are useful not only for their good optical properties such as refractive index, birefringence, and Abbe number, and good heat resistance as indicated by glass transition temperature, but also for their readily available raw materials.

[0363] As can be confirmed from manufacturing examples 6 and 7, when the copolymerization ratio of compound 3 increases, the glass transition temperature of the resin increases significantly. Therefore, the resin using compound 3 (included in the compound shown in general formula (1b)) is suitable for applications requiring high heat resistance.

[0364] As can be seen from manufacturing example 9, the resin using compound 5 (included in the compound shown in general formula (1c)) has a low birefringence intensity, and therefore has the advantage of being easy to fine-tune the copolymerization ratio with the combined monomers so that the birefringence of the resin obtained by copolymerization is zero. As a result, the birefringence of the resin can be made infinitely close to zero.

[0365] Industrial availability

[0366] The cyclic diol compounds of the present invention can be used as raw material monomers and modifiers for resins such as polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, and polymethacrylate resins. They are particularly suitable as polycarbonate resins containing structural units derived from these cyclic diol compounds. Furthermore, the cyclic diol compounds of the present invention can be used as resin modifiers to widely adjust the glass transition temperature, refractive index, birefringence, Abbe number, and other physical properties of resins. Therefore, they are 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 (1a), This resin modifier is a reagent used as a raw material monomer for polyester carbonate resin or polycarbonate resin to modify the physical properties of the resin. In formula (1a), R 1 are identical or different, each is a methyl or ethyl group, and R 2 are identical or different, each is a hydrogen atom, a methyl or ethyl group.

2. A resin modifier comprising a compound represented by general formula (1c), This resin modifier is a reagent used as a raw material monomer for polyester carbonate resin or polycarbonate resin to modify the physical properties of the resin. In equation (1c), R 1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

3. The compound represented by general formula (1a), In equation (1a), R 1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

4. The compound represented by general formula (1c), In equation (1c), R 1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

5. A method for producing a compound of general formula (1a), comprising the step of reacting a compound of general formula (3a) with a compound of general formula (4), In the formula, R 1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

6. A method for producing a compound of general formula (1c), comprising the step of reacting a compound of general formula (3c) with a compound of general formula (4), In the formula, R 1 Whether they are the same or different, each is methyl or ethyl, R 2 They may be the same or different, each consisting of a hydrogen atom, a methyl group, or an ethyl group.

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