JP7640870B2 - Cyclic diol compound, method for producing said compound and use of said compound - Google Patents

Description

The present invention relates to a cyclic diol compound, a method for producing the compound, and uses of the compound.

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.

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

However, the properties of resins such as polyester resins and polycarbonate resins vary widely depending on the various fields of application in which the resins are used, and the search is on for cyclic diol compounds that can satisfy the resin properties required in these fields. In particular, when resins are used for optical applications, there is a demand for cyclic diol compounds that can improve the optical properties of the resins.

JP 2012-214803 A JP 2013-001867 A

The present invention aims to provide a modifier for resins such as polyester resins, polyester carbonate resins, and polycarbonate resins. Another objective of the present invention is to provide a cyclic diol compound useful as a resin modifier and a method for producing the same.

The present inventors conducted intensive research to solve the above problems and 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 with new physical properties. Specifically, the inventors 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 acid ester resins, polymethacrylic acid ester resins, and polyester polyol resins. Based on this knowledge, the inventors conducted further research and completed the present invention.

That is, the present invention provides a resin modifier comprising the following cyclic diol compound, a cyclic diol compound, and a method for producing the compound.

［式中、Ｒ^１は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、フェニル基又は炭素数１～４の直鎖状若しくは分岐鎖状のアルキル基を示す。環Ａは、フッ素原子、塩素原子、臭素原子、フェニル基、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、及び炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基からなる群から選択される１～４個の基で置換されていてもよいベンゼン環を示す。］
［項２］
樹脂改質剤が、ポリエステル樹脂、ポリエステルカーボネート樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂及びポリエステルポリオール樹脂からなる群より選択される１以上の樹脂の改質剤である、［項１］に記載の樹脂改質剤。
［項３］
一般式（１）において、Ｒ^１が、同一又は異なって、それぞれ、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基又はフェニル基である、［項１］又は［項２］に記載の樹脂改質剤。
［項４］
一般式（１）において、Ｒ^１が、同一又は異なって、それぞれ、メチル基又はエチル基である、［項３］に記載の樹脂改質剤。
［項５］
一般式（１）において、環Ａが、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、及び炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基からなる群から選択される１～４個の基で置換されていてもよいベンゼン環である、［項１］～［項４］のいずれかに記載の樹脂改質剤。
［項６］
一般式（１）において、Ｒ^１が、メチル基又はエチル基であり、環Ａが、メチル基及びエチル基からなる群から選択される１～４個の基で置換されていてもよいベンゼン環である、［項１］～［項５］のいずれかに記載の樹脂改質剤。
［項７］
一般式（１）において、環Ａが、ベンゼン環である、［項１］～［項６］のいずれかに記載の樹脂改質剤。
［項８］
一般式（１）で表される化合物が、一般式（１ａ）で表される化合物である、［項１］又は［項２］に記載の樹脂改質剤。

［式中、Ｒ^２は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、フェニル基、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、又は炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基を示す。Ｒ^１は、前記に同じ。］
［項９］
一般式（１）で表される化合物が、一般式（１ｂ）で表される化合物である、［項１］又は［項２］に記載の樹脂改質剤。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項１０］
一般式（１）で表される化合物が、一般式（１ｃ）で表される化合物である、［項１］又は［項２］に記載の樹脂改質剤。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項１１］
一般式（１）で表される化合物からなる樹脂原料用モノマー。
［項１２］
一般式（１ａ）で表される化合物。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項１３］
一般式（１ｃ）で表される化合物。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項１４］
Ｒ^１が、同一又は異なって、それぞれ、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基又はフェニル基である、［項１２］又は［項１３］に記載の化合物。
［項１５］
Ｒ^１が、同一又は異なって、それぞれ、メチル基又はエチル基である、［項１４］に記載の化合物。
［項１６］
Ｒ^２が、同一又は異なって、それぞれ、水素原子、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、又は炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基である、［項１２］～［項１５］のいずれかに記載の化合物。
［項１７］
Ｒ^１が、同一又は異なって、それぞれ、メチル基又はエチル基であり、Ｒ^２が、同一又は異なって、それぞれ、水素原子、メチル基又はエチル基である、［項１２］～［項１６］のいずれかに記載の化合物。
［項１８］
Ｒ^２が、すべて水素原子である、［項１２］～［項１７］のいずれかに記載の化合物。
［項１９］
一般式（１）で表される化合物の製造方法であって、一般式（３）で表される化合物と一般式（４）で表される化合物とを反応（アセタール化反応）させる工程を含む、製造方法。

［式中、Ｒ^１及び環Ａは、前記に同じ。］
［項２０］
一般式（１ａ）で表される化合物の製造方法であって、一般式（３ａ）で表される化合物と一般式（４）で表される化合物とを反応（アセタール化反応）させる工程を含む、製造方法。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項２１］
一般式（１ｃ）で表される化合物の製造方法であって、一般式（３ｃ）で表される化合物と一般式（４）で表される化合物とを反応（アセタール化反応）させる工程を含む、製造方法。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項２２］
一般式（２）で表される構成単位（繰り返し単位）を含有するポリカーボネート樹脂。

［式中、Ｒ^１及び環Ａは、前記に同じ。］
［項２３］
一般式（２ａ）で表される構成単位（繰り返し単位）を含有する［項２２］に記載のポリカーボネート樹脂。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項２４］
一般式（２ｃ）で表される構成単位（繰り返し単位）を含有する［項２２］に記載のポリカーボネート樹脂。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項２５］
一般式（２ｂ）で表される構成単位（繰り返し単位）を含有する［項２２］に記載のポリカーボネート樹脂。

［式中、Ｒ^１及びＲ^２は、前記に同じ。］
［項２６］
ポリエステル樹脂、ポリエステルカーボネート樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂及びポリエステルポリオール樹脂からなる群より選択される１以上の樹脂を製造するための、一般式（１）で表される化合物の使用。
［項２７］
一般式（１）で表される化合物を、ポリエステル樹脂、ポリエステルカーボネート樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂及びポリエステルポリオール樹脂からなる群より選択される１以上の樹脂の（原料である）モノマーとして使用する方法。
［項２８］
ポリエステル樹脂、ポリエステルカーボネート樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂及びポリエステルポリオール樹脂からなる群より選択される１以上の樹脂を改質するための、一般式（１）で表される化合物のモノマーとしての使用。
［項２９］
一般式（１）で表される化合物を含むモノマーを用いて、ポリエステル樹脂、ポリエステルカーボネート樹脂、ポリカーボネート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂及びポリエステルポリオール樹脂からなる群より選択される１以上の樹脂を改質する方法。 [Item 1]
A resin modifier comprising a compound represented by general formula (1) (hereinafter also referred to as a "cyclic diol compound").

[In the formula, R ¹ may be 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 which may 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.]
[Item 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].
[Item 3]
In the general formula (1), R ¹ is the same or different and 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. The resin modifier according to [Item 1] or [Item 2].
[Item 4]
In the general formula (1), R ¹ is the same or different and is a methyl group or an ethyl group.
[Item 5]
In the 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. [Item 1] to [Item 4] are resin modifiers according to any one of the above.
[Item 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. [Item 1] to [Item 5] are described in any one of the resin modifiers.
[Item 7]
In the general formula (1), ring A is a benzene ring. The resin modifier according to any one of [1] to [6].
[Item 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).

[In the formula, R ² may be 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. ^{R 1} is the same as above.]
[Item 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).

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 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):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 11]
A resin raw material monomer comprising a compound represented by general formula (1):
[Item 12]
A compound represented by general formula (1a):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 13]
A compound represented by general formula (1c):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 14]
The compound according to [Item 12] or [Item 13], wherein R ¹ is the same or different and 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.
[Item 15]
The compound according to [Item 14], wherein R ¹ is the same or different and is a methyl group or an ethyl group.
[Item 16]
The compound according to any one of [Item 12] to [Item 15], wherein R ² is the same or different and 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.
[Item 17]
The compound according to any one of [Item 12] to [Item 16], wherein R ¹ is the same or different and is a methyl group or an ethyl group, and R ² is the same or different and is a hydrogen atom, a methyl group, or an ethyl group.
[Item 18]
The compound according to any one of [Item 12] to [Item 17], wherein all of R ² 's are hydrogen atoms.
[Item 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).

[In the formula, ^R1 and ring A are the same as above.]
[Item 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).

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 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).

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 22]
A polycarbonate resin containing a structural unit (repeating unit) represented by general formula (2).

[In the formula, ^R1 and ring A are the same as above.]
[Item 23]
The polycarbonate resin according to [22], which contains a structural unit (repeating unit) represented by general formula (2a):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 24]
The polycarbonate resin according to [22], which contains a structural unit (repeating unit) represented by general formula (2c):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 25]
The polycarbonate resin according to [22], which contains a structural unit (repeating unit) represented by general formula (2b):

[In the formula, ^R1 and ^R2 are the same as above.]
[Item 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.
[Item 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 acid ester resins, polymethacrylic acid ester resins, and polyester polyol resins.
[Item 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.
[Item 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 acid ester resins, polymethacrylic acid ester resins, and polyester polyol resins, using a monomer containing a compound represented by general formula (1).

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.

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.).

1 is an IR spectrum of isophthalaldehyde trimethylolethane diacetal (compound 1) obtained in Example 1. 1 is a ¹ H-NMR spectrum of isophthalaldehyde trimethylolethane diacetal (compound 1) obtained in Example 1. 1 is an IR spectrum of isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2. 1 is a ¹ H-NMR spectrum of isophthalaldehyde trimethylolpropane diacetal (compound 2) obtained in Example 2. 1 is an IR spectrum of terephthalaldehyde trimethylolethane diacetal (compound 3) obtained in Example 3. 1 is a ¹ H-NMR spectrum of terephthalaldehyde trimethylolethane diacetal (compound 3) obtained in Example 3. 1 is an IR spectrum of terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4. 1 is a ¹ H-NMR spectrum of terephthalaldehyde trimethylolpropane diacetal (compound 4) obtained in Example 4. 1 is an IR spectrum of ortho-phthalaldehyde trimethylolethane diacetal (compound 5) obtained in Example 5. 1 is a ¹ H-NMR spectrum of ortho-phthalaldehyde trimethylolethane diacetal (compound 5) obtained in Example 5.

［式中、Ｒ^１は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、フェニル基又は炭素数１～４の直鎖状若しくは分岐鎖状のアルキル基を示す。環Ａは、フッ素原子、塩素原子、臭素原子、フェニル基、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、及び炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基からなる群から選択される１～４個の基で置換されていてもよいベンゼン環を示す。］ 1. Resin Modifier The resin modifier of the present invention comprises a compound represented by general formula (1).

[In the formula, R ¹ may be 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 which may 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.]

In general formula (1), R ¹ may be the same or different and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, or a phenyl group. The linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ 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. Of 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.

［式中、環Ａは前記に同じ。］ 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:

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

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.

The substituent "linear or branched alkoxy group having 1 to 6 carbon atoms" is not particularly limited, and examples thereof include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy. Among these, methoxy, ethoxy, isopropyloxy, isobutyloxy, and tert-butyloxy are preferred.

The substituent "linear or branched alkyl group having 1 to 6 carbon atoms" is not particularly limited, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Of these, methyl, ethyl, isopropyl, isobutyl, and tert-butyl groups are preferred.

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

The compound represented by the general formula (1) may have a number of stereoisomers based on the configuration of the carbon atom to which the hydroxymethyl group in the two acetal groups and R ¹ are bonded. These isomers may exist alone or in mixture.

Resins to which the resin modifier of the present invention is applied are not particularly limited as long as they contain a repeating unit (structural unit) derived from a cyclic diol compound represented by general formula (1), that is, a divalent repeating unit obtained by removing the hydrogen atom of a hydroxyl group from a cyclic diol compound represented by general formula (1), and examples thereof include 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 are polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferably polyester carbonate resins and polycarbonate resins.

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), namely, the compounds represented by the following general formulas (1a), (1b), and (1c), will be specifically described below.

［式中、Ｒ^２は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、フェニル基、炭素数１～６の直鎖状若しくは分岐鎖状のアルコキシ基、又は炭素数１～６の直鎖状若しくは分岐鎖状のアルキル基を示す。Ｒ^１は、前記に同じ。］ The compound represented by the general formula (1a) is as follows.

[In the formula, R ² may be 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. ^{R 1} is the same as above.]

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.

In general formula (1a), ^R2 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. ^R2 is particularly preferably a hydrogen atom.
The "straight or branched alkoxy group having 1 to 4 carbon atoms" represented by ^R2 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.

The "straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms" represented by ^R2 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.

［式中、Ｒ^１及びＲ^２は前記に同じ。］ The compound represented by the general formula (1a) may have isomers such as the following isomer A, isomer B, or isomer C. These isomers may be present alone or in admixture.

[In the formula, ^R1 and ^R2 are the same as above.]

When the compound represented by 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 taken as the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

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

Specific examples of the compound represented by 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, 4-chloroisophthalaldehyde trimethylolethane diacetal, 5-bromoisophthalaldehyde trimethylolethane diacetal, 4-bromoisophthalaldehyde trimethylolethane diacetal, 4,6-dimethylisophthalaldehyde trimethylolethane diacetal, 2,4-dimethylisophthalaldehyde trimethylolethane diacetal, 4-bromoisophthalaldehyde trimethylolethane diacetal, 4-bromoisophthalaldehyde trimethylolethane diacetal, 4,6-dimethylisophthalaldehyde trimethylolethane diacetal, 4-bromo ... Tyrrolethane diacetal, 2,5-dichloroisophthalaldehyde trimethylolethane diacetal, 4,6-dichloroisophthalaldehyde 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-isopropylisophthalaldehyde trimethylolethane diacetal, 4,6-diisopropylisophthalaldehyde trimethylolethane diacetal, 2-bromo-5-tert-butylisophthalaldehyde isophthalaldehyde trimethylol ethane diacetal, 4-phenylisophthalaldehyde trimethylol ethane diacetal, 5-phenylisophthalaldehyde trimethylol ethane diacetal, 4-phenyl-6-methylisophthalaldehyde trimethylol ethane diacetal, 4,5-diethyl-6-methylisophthalaldehyde trimethylol ethane diacetal, 5-hexylisophthalaldehyde trimethylol ethane diacetal, 4-hexylisophthalaldehyde trimethylol ethane diacetal, 5-butyloxyisophthalaldehyde trimethylol ethane diacetal, 2-methoxyisophthalaldehyde trimethylol ethane diacetal, 4-methoxyisophthalaldehyde trimethylol ethane diacetal, 5-methoxyisophthalaldehyde trimethylol ethane 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 trimethylolethane diacetal, 2,4-dimethoxy-6-methylisophthalaldehyde trimethylolethane diacetal, 2,4-dimethyl-6-methoxyisophthalaldehyde trimethylolethane diacetal, 4-ethyl-5-methylisophthalaldehyde ethyl-6-methoxyisophthalaldehyde trimethylolethane diacetal, 5-methylisophthalaldehyde trimethylolpropane diacetal, 4-methylisophthalaldehyde trimethylolpropane diacetal, 4-chloroisophthalaldehyde trimethylolpropane diacetal, 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 isophthalaldehyde 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 trimethylolpropane diacetal, 2-bromo-5-tert-butylisophthalaldehyde trimethylolpropane diacetal, 4-phenylisophthalaldehyde trimethylolpropane diacetal, 5-phenylisophthalaldehyde isophthalaldehyde trimethylolpropane diacetal, 4-phenyl-6-methyl isophthalaldehyde trimethylolpropane diacetal, 4,5-diethyl-6-methyl isophthalaldehyde trimethylolpropane diacetal, 5-hexyl isophthalaldehyde trimethylolpropane diacetal, 4-hexyl isophthalaldehyde trimethylolpropane diacetal, 5-butyloxy isophthalaldehyde trimethylolpropane diacetal, 2-methoxyisophthalaldehyde trimethylolpropane diacetal, 4-methoxyisophthalaldehyde trimethylolpropane diacetal, 5-methoxyisophthalaldehyde trimethylolpropane diacetal, 2-methoxy-4-methyl isophthalaldehyde trimethylolpropane diacetal, 2-methyl-4-methoxyisophthalaldehyde Examples of the isophthalaldehyde trimethylolpropane diacetal include soft aldehyde trimethylolpropane diacetal, 2-methoxy-5-methyl isophthalaldehyde trimethylolpropane diacetal, 4-methyl-6-methoxy isophthalaldehyde trimethylolpropane diacetal, 4,6-dimethoxy isophthalaldehyde trimethylolpropane diacetal, 2-methoxy-4-ethyl isophthalaldehyde trimethylolpropane diacetal, 4,6-dimethyl-2-methoxy isophthalaldehyde trimethylolpropane diacetal, 2,4-dimethoxy-6-methyl isophthalaldehyde trimethylolpropane diacetal, 2,4-dimethyl-6-methoxy isophthalaldehyde trimethylolpropane diacetal, and 4-ethyl-5-methyl-6-methoxy isophthalaldehyde trimethylolpropane diacetal. Among these, 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, and the like. Particularly preferred compounds include isophthalaldehyde trimethylolpropane diacetal, isophthalaldehyde trimethylolethane diacetal, and the like.

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ The compound represented by the general formula (1b) is as follows.

[In the formula, ^R1 and ^R2 are the same as above.]

Preferred ^R1 in formula (1b) is the same as preferred ^R1 in formula (1a). Preferred ^R2 in formula (1b) is the same as preferred ^R2 in formula (1a).

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ 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.

[In the formula, ^R1 and ^R2 are the same as above.]

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 taken as the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

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

Specific examples of the compound represented by general formula (1b) include, for example, terephthalaldehyde trimethylolpropane diacetal, terephthalaldehyde trimethylolethane diacetal, 2-methylterephthalaldehyde trimethylolethane diacetal, 3-methylterephthalaldehyde trimethylolethane diacetal, 3-chloroterephthalaldehyde trimethylolethane diacetal, 2-chloroterephthalaldehyde trimethylolethane diacetal, 2-bromoterephthalaldehyde trimethylolethane diacetal, 3-bromoterephthalaldehyde trimethylolethane diacetal, 3,6-dimethylterephthalaldehyde trimethylolethane diacetal, and 2,3-dimethylterephthalaldehyde trimethylolethane diacetal. terephthalaldehyde, 2,5-dichloroterephthalaldehyde trimethylol ethane diacetal, 3,6-dichloroterephthalaldehyde 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-diisopropylterephthalaldehyde trimethylol ethane diacetal, 2-bromo-5-tert-butylterephthalaldehyde trimethylol ethane diacetal, 3-phenyl Terephthalaldehyde trimethylolethane diacetal, 2-phenylterephthalaldehyde trimethylolethane diacetal, 3-phenyl-6-methylterephthalaldehyde trimethylolethane 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 terephthalaldehyde, 2-methyl-3-methoxyterephthalaldehyde trimethylol ethane diacetal, 2-methoxy-5-methylterephthalaldehyde trimethylol ethane diacetal, 3-methyl-6-methoxyterephthalaldehyde trimethylol ethane diacetal, 3,6-dimethoxyterephthalaldehyde trimethylol ethane diacetal, 2-methoxy-3-ethylterephthalaldehyde trimethylol ethane diacetal, 3,6-dimethyl-2-methoxyterephthalaldehyde trimethylol ethane diacetal, 2,3-dimethoxy-6-methylterephthalaldehyde trimethylol ethane diacetal, 2,3-dimethyl-6-methoxyterephthalaldehyde trimethylol ethane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde terephthalaldehyde 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 terephthalaldehyde trimethylolpropane diacetal, 3,6-dibromo terephthalaldehyde trimethylolpropane diacetal, 2,5-dibromo terephthalaldehyde trimethylolpropane diacetal, 2-tert-butyl terephthalaldehyde trimethylolpropane diacetal, 2,3,5,6-tetrafluoro terephthalaldehyde trimethylolpropane diacetal, 3-isopropyl terephthalaldehyde trimethylolpropane diacetal, 3,6-diisopropyl terephthalaldehyde trimethylolpropane diacetal, 2-bromo-5-tert-butyl terephthalaldehyde trimethylolpropane diacetal, 3-phenyl terephthalaldehyde trimethylolpropane diacetal, 2-phenyl terephthalaldehyde trimethylolpropane diacetal Tyrolpropane diacetal, 3-phenyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 3,5-diethyl-6-methylterephthalaldehyde trimethylolpropane diacetal, 2-hexylterephthalaldehyde trimethylolpropane diacetal, 3-hexylterephthalaldehyde trimethylolpropane 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 acetal, 3-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxyterephthalaldehyde trimethylolpropane diacetal, 2-methoxy-3-ethyl terephthalaldehyde trimethylolpropane diacetal, 2-methoxy-5-methyl terephthalaldehyde trimethylolpropane diacetal, 3,6-dimethyl-2-methoxyterephthalaldehyde trimethylolpropane diacetal, 2,3-dimethoxy-6-methyl terephthalaldehyde trimethylolpropane diacetal, 2,3-dimethyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, 3-ethyl-5-methyl-6-methoxyterephthalaldehyde trimethylolpropane diacetal, and the like. Among these, 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, and the like. Particularly preferred compounds include terephthalaldehyde trimethylolpropane diacetal, terephthalaldehyde trimethylolethane diacetal, and the like.

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ The compound represented by general formula (1c) is as follows.

[In the formula, ^R1 and ^R2 are the same as above.]

Preferred ^R1 in formula (1c) is the same as preferred ^R1 in formula (1a). Preferred ^R2 in formula (1c) is the same as preferred ^R2 in formula (1a).

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ The compound represented by formula (1c) may have isomers such as isomer (1c-A), isomer (1c-B), or isomer (1c-C) as shown below. These isomers may exist alone or in mixture.

[In the formula, ^R1 and ^R2 are the same as above.]

When the compound represented by 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 taken as the isomer ratio. The cyclic diol compound of the present invention can also be subjected to trimethylsilylation of the hydroxyl groups using N,O-bis(trimethylsilyl)trifluoroacetamide or the like, followed by GC analysis.

The compound represented by general formula (1c) may have isomers such as isomer (1c-A), isomer (1c-B), or isomer (1c-C) as described above. Two or three isomer peaks were detected by GC analysis, and these are considered to be isomer (1c-A), isomer (1c-B), or isomer (1c-C). The isomer ratio by GC analysis may be in the range of isomer (1c-A):isomer (1c-B):isomer (1c-C) = 10 to 1:10 to 1:1.

Specific examples of compounds represented by 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 Aldehyde trimethylolethane diacetal, 3,4-dimethyl orthophthalaldehyde trimethylolethane diacetal, 3,5-dimethyl orthophthalaldehyde trimethylolethane diacetal, 4,5-dimethyl orthophthalaldehyde trimethylolethane diacetal, 3,6-dichloro orthophthalaldehyde trimethylolethane diacetal, 3,6-dibromo orthophthalaldehyde trimethylolethane diacetal, 3,6-diethyl-4-methyl orthophthalaldehyde trimethylol 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 trimethylolethane 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 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 Methylolpropane diacetal, 3,6-diethyl-4-methyl orthophthalaldehyde trimethylolpropane 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 orthophthalaldehyde trimethylolpropane diacetal, 3,6-dimethoxy 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 Examples of the compounds include 3-methyl-o-phthalaldehyde trimethylolethane diacetal, 3-methyl-o-phthalaldehyde trimethylolethane diacetal, 3-methyl-o-phthalaldehyde trimethylolpropane diacetal, 4-methyl-o-phthalaldehyde trimethylolpropane diacetal, 4-methyl-o-phthalaldehyde trimethylolethane diacetal, and the like. Particularly preferred compounds include ortho-phthalaldehyde trimethylolpropane diacetal, ortho-phthalaldehyde trimethylolethane diacetal, and the like.

［式中、Ｒ^１及び環Ａは、前記に同じ。］
具体的には、一般式（１）で表される化合物は、一般式（３）で表される化合物と、一般式（４）で表される化合物とを、酸性触媒の存在下で反応（アセタール化反応）させることにより製造することができる。 2. Method for Producing 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 represented by general formula (3) can be produced through a step of reacting (acetalization reaction) a compound represented by general formula (4).

[In the formula, ^R1 and ring A are 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).

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 known acid catalysts can be used. Examples of the acid catalyst include 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 moles, and preferably about 0.8 to 2 moles, per mole of the compound represented by formula (3).

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ 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>.

[In the formula, ^R1 and ^R2 are the same as above.]

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ 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>.

[In the formula, ^R1 and ^R2 are the same as above.]

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ 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>.

[In the formula, ^R1 and ^R2 are the same as above.]

3. Production of resin using resin modifier The compound represented by the general formula (1) (cyclic diol compound) 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 are polyester resins, polyester carbonate resins, polycarbonate resins, and polyurethane resins, and more preferred are polyester carbonate resins and polycarbonate resins.

［式中、Ｒ^１及び環Ａは、前記に同じ。］ 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).

[In the formula, ^R1 and ring A are the same as above.]

In formula (2), specific examples and preferred examples of R ¹ and ring A are the same as the specific examples and preferred examples of R ¹ and ring A described in formula (1).

［式中、Ｒ^１及びＲ^２は、前記に同じ。］ 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 formulas (2a), (2b), and (2c), respectively.

[In the formula, ^R1 and ^R2 are the same as above.]

［式中、Ｒ^１及びＲ^２は、前記に同じ。］

[In the formula, ^R1 and ^R2 are the same as above.]

［式中、Ｒ^１及びＲ^２は、前記に同じ。］

[In the formula, ^R1 and ^R2 are the same as above.]

In the case of a polycarbonate resin containing a repeating unit (structural unit) represented by general formula (2), it can be produced by (polymerizing) a raw material monomer containing a compound represented by general formula (1) with a carbonyl precursor compound.

As a raw material monomer for polycarbonate resin, the compound represented by general formula (1) can be used alone. 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 structural unit represented by general formula (2). As such a homopolymer, a homopolymer having a structural unit represented by general formula (2a) or a structural unit represented by general formula (2c) is preferable.

In addition to the compound represented by general formula (1), the raw material monomer for polycarbonate resin may contain a dihydroxy compound that is generally used as a structural unit of polycarbonate resin. Examples of the dihydroxy compound include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.

In other words, the polycarbonate resin may be a copolymer that contains 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). A copolymer having multiple types of structural units may be either a block copolymer or a random copolymer.

Examples of aliphatic dihydroxy compounds include various ones, 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-dioxane-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and the like.

Aromatic dihydroxy compounds include a variety of 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. Other examples include hydroquinone, resorcinol, and catechol.

The proportion of the compound represented by general 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% of the total amount of monomers. In other words, in the polycarbonate resin, the proportion of the structural unit represented by general formula (2) derived from the compound represented by general 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% of the total amount of structural units.

Examples of carbonyl precursor compounds include phosgene, triphosgene, diphenyl carbonate, etc.

［式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、メチル基又はエチル基を表し、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、メチル基、エチル基、又は炭素数２～５のアルキレングリコールから１つの水酸基を除いて得られる一価の基を表す。］ 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. As the raw material monomer, for example, one containing a structural unit derived from at least one monomer selected from the following monomer group is also preferred.

[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.]

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. Copolymers having multiple types of structural units may be either block copolymers or random copolymers.

The number average molecular weight (Mn) of the polycarbonate resin or polyester carbonate resin containing the structural unit represented by general formula (2) is about 4000 to 100,000, preferably about 10,000 to 50,000, the weight average molecular weight (Mw) is about 5,000 to 100,000, preferably about 6,000 to 80,000, 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.

The refractive index (n _D ) of a polycarbonate resin or polyester carbonate resin containing a structural unit represented by general formula (2) 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.

The Abbe number (ν _d ) of birefringence of a polycarbonate resin or polyester carbonate resin containing a structural unit represented by general formula (2) 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.

4. Uses of modified resins The compound represented by formula (1) can be polymerized as a single monomer or as a copolymerization monomer 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 formula (1) added and copolymerizing it with other monomers.

Therefore, the resin obtained using the resin modifier of the present invention can be suitably used for optical components, for example. Optical components 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 components. In a preferred embodiment of the present invention, optical components manufactured using the resin of the present invention include optical lenses, optical films, optical sheets, etc.

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 are therefore extremely useful in fields where expensive high refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors.

In addition, by adjusting the content of the structural units derived from the compound represented by general formula (1), the refractive index of the resin of the present invention can be adjusted over a wide range to suit the design of various optical lenses.

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 films for liquid crystal substrates, optical memory cards, etc.

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.

When resins for optical components have large birefringence, the optical distortion increases, so when they are used for optical lenses, for example, problems such as bleeding and blurring occur. For this reason, there is a demand for smaller birefringence to provide a clearer view.

There are various resins commonly used for optical components, including polyester resin, polyester carbonate resin, polycarbonate resin, etc., with polyester carbonate resin and polycarbonate resin in particular being excellent in transparency, impact resistance, heat resistance, dimensional stability, etc.

More specifically, resins (particularly polycarbonate resins) homopolymerized or copolymerized using a compound represented by general formula (1) have the 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 by copolymerizing a structural unit derived from a compound represented by general formula (1) with a structural unit of another dihydroxy compound, a resin with birefringence close to zero can be produced. The resin can be suitably used in applications where the birefringence needs to be as close to zero as possible, particularly as optical components such as optical lenses, optical films, and optical sheets. Applicable optical components are not particularly limited, but examples include smartphone camera lenses, vehicle-mounted camera lenses, goggle lenses for VR (virtual reality) or MR (mixed reality), and security camera lenses.

In this specification, the expressions "comprise" and "contain" include the meanings of "consisting essentially of" and "consisting only of".

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 cyclic diol compounds were performed by the following methods. Reagents were used for compounds not specifically mentioned.

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

<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.

[Measurement conditions]
Equipment: Shimadzu GC-2020
Column: Agilent Technologies DB-1 30m x 0.25mm x 0.25μm
Column temperature: 80°C (holding time 5 min) - heating rate 10°C/min - 320°C (holding time 5 min)
Injection temperature/detector temperature: 300°C/325°C
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: 30 cm/sec
Injection volume: 1 μl

<Melting Point>
The melting point of the cyclic diol compound was measured using a differential calorimeter DSC6220 manufactured by SII NanoTechnology Inc. 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 indicated by the peak top was taken as the melting point.

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

<Proton Nuclear Magnetic Resonance Spectrum ( ¹ H-NMR)>
¹ H-NMR of the cyclic diol compound was measured by dissolving it in a deuterated solvent (deuterated chloroform or deuterated methanol) and then using a nuclear magnetic resonance apparatus (DRX-500, ¹ H-NMR (500 MHz) manufactured by Bruker).
In addition, a water peak may be observed in the solvent used for ¹ H-NMR measurement. The peak due to water contained in deuterated chloroform is present at about 1.56 ppm, and the peak due to water contained in deuterated methanol is present at about 4.87 ppm.

<Glass transition temperature>
The glass transition temperature of the obtained polycarbonate resin was measured using a differential calorimeter DSC6220 manufactured by SII Nanotechnology, Inc. 6.7 mg of the sample was placed in an aluminum pan manufactured by the same company and sealed, and the sample was heated from 30°C to 220°C at a heating rate of 10°C/min under a nitrogen 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.

<Number average molecular weight, weight average molecular weight and polydispersity index>
About 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) containing approximately 0.025% BHT, manufactured by Nacalai Tesque, Inc. Column temperature: 40°C
Flow rate: 1.0mL/min
Injection volume: 100 μl
Analysis method: PS-equivalent molecular weight Standard polymer used: Shodex STANDARD SM-105

<Refractive index>
The polycarbonate resin obtained in each of the production 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 that, the resin was cooled for 3 minutes to obtain a polycarbonate film having a thickness of 0.1 mm.
A rectangular test piece 40 mm long and 8 mm wide was cut out from this 0.1 mm thick film to prepare a measurement sample. The refractive index _nD was measured according to the method of JIS-K-7142 using an interference filter with a wavelength of 589 nm (D line) and a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. Diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as an intermediate liquid for the measurement.

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

<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 in "Refractive Index" to prepare a measurement sample. The refractive indices nC, nD, and nF at each wavelength were measured by 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, and the Abbe number _νd was calculated from these measured values and the following formula.
vD=(nD-1)/(nF-nC)
In the measurements, diiodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the intermediate liquid.

<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 stretched film was measured for retardation at each wavelength of 449.9, 498.0, 548.0, 588.8, 628.8, and 751.0 nm using a HAYASHI-REPIC Corporation-manufactured Luminous Ace LA-100USW light source device 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 obtained and the film thickness of the stretched film according to the following formula. In addition, 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 a measurement wavelength of 588.8 nm [nm])/(Film thickness [mm]×10 ⁶ )

<Synthesis of Cyclic Diol Compound>
[Example 1]
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, 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 generated crystals were filtered off, and the obtained crystals were first rinsed twice with 50ml of ion-exchanged water, and 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 subjected to IR and ^1H -NMR spectroscopy. 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.

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

[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, and 60ml of toluene was distilled off under reduced pressure, after which 150g of ion-exchanged water was added and cooled with ice water. The resulting crystals were filtered off, and the crystals were first rinsed twice with 50ml of ion-exchanged water, and 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 100ml of water was added after distilling off 40g of isopropyl alcohol. The precipitated crystals were separated by filtration, 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) having a purity of 98.5% (GC area percentage). The melting point of the crystals was 95.5° C.
The obtained isophthalaldehyde trimethylolpropane diacetal was subjected to IR and ^1H -NMR spectroscopy. 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 product was isophthalaldehyde trimethylolpropane diacetal.

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

[Example 3]
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 (0.22 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 H-NMR spectrum of the obtained terephthalaldehyde trimethylolethane diacetal were 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.

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

[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 about 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 H-NMR spectrum of the obtained terephthalaldehyde trimethylolpropane diacetal were 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.

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

[Example 5]
Into a 1000 mL four-neck flask equipped with a stirrer, a thermometer, and a Dean-Stark with a condenser, 40.2 g (0.3 mol), 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 were added, and the mixture was heated and stirred under reflux conditions for about 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, neutralized with 25 ml of saturated sodium bicarbonate, and 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 performed twice in total. The obtained organic layer 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 IR spectrum and ¹ H-NMR spectrum of the obtained ortho-phthalaldehyde trimethylolethane diacetal were 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 product was ortho-phthalaldehyde trimethylolethane diacetal.

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

<Production of Resin and Evaluation of Physical Properties>
[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 bisphenoxyethanolfluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 283.29 μL (70.8 × 10 ^-7 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after 20 minutes of holding, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") was taken out. During the reaction, phenol by-product 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 25.6. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 2] (Production of Polycarbonate Resin 2)
7.6 g (0.02 mol) of compound 1 obtained in Example 1, 23.0 g (0.05 mol) of bisphenoxyethanolfluorene, 16.5 g (0.08 mol) of diphenyl carbonate, and 30.2 μL (76.1 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after holding for 20 minutes, 28 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") was taken out. During the reaction, phenol 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 26.8. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 3] (Production of Polycarbonate Resin 3)
23.0 g (0.07 mol) of compound 1 obtained in Example 1, 29.8 g (0.07 mol) of bisphenoxyethanolfluorene, 29.9 g (0.14 mol) of diphenyl carbonate, and 54.9 μL (137.2 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after holding for 20 minutes, 35 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") was taken out. During the reaction, phenol 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 28.5. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 4] (Production of Polycarbonate Resin 4)
15.4 g (0.05 mol) of compound 1 obtained in Example 1, 10.0 g (0.05 mol) of diphenyl carbonate, and 18.4 μL (46.0 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were placed in a 300 mL four-neck flask equipped with a stirrer and a distillation apparatus, and the mixture was stirred under a nitrogen atmosphere and heated to 200 ° C.
After the substrate was dissolved, the temperature was raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after 20 minutes of holding, 12 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 4") was taken out. During the reaction, phenol 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 43.0. The total light transmittance was 92%. The results are shown in Table 1.

[Production Example 5] (Production of Polycarbonate Resin 5)
10.4 g (0.03 mol) of compound 2 obtained in Example 2, 49.9 g (0.11 mol) of bisphenoxyethanolfluorene, 31.3 g (0.15 mol) of diphenyl carbonate, and 286.9 μL (717.0 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after 20 minutes of holding, 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") was taken out. During the reaction, phenol by-product was distilled off. The taken-out polycarbonate resin 5 was pulverized, and the glass transition temperature was measured 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[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 bisphenoxyethanolfluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 283.6 μL (70.9 × 10 ^-7 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 6") was taken out after 20 minutes of holding. During the reaction, phenol by-product 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 7] (Production of Polycarbonate Resin 7)
13.8 g (0.04 mol) of compound 3 obtained in Example 3, 41.8 g (0.09 mol) of bisphenoxyethanolfluorene, 30.0 g (0.14 mol) of diphenyl carbonate, and 55.0 μL (137.5 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after 20 minutes of holding, 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 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 27.5. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 8] (Production of Polycarbonate Resin 8)
10.6 g (0.02 mol) of compound 4 obtained in Example 4, 49.2 g (0.11 mol) of bisphenoxyethanolfluorene, 30.9 g (0.15 mol) of diphenyl carbonate, and 283.5 μL (70.9 × 10 ^-7 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and 45 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 8") was taken out after 20 minutes of holding. 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 25.7. The total light transmittance was 90%. The results are shown in Table 1.

[Production Example 9] (Production of Polycarbonate Resin 9)
5.8 g (0.02 mol) of compound 5 obtained in Example 5, 30.3 g (0.07 mol) of bisphenoxyethanolfluorene, 19.1 g (0.09 mol) of diphenyl carbonate, and 34.9 μL (87.3 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium hydrogen carbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and 25 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin 9") was taken out after 20 minutes of holding. During the reaction, phenol by-product was distilled off. The polycarbonate resin 9 taken out was pulverized, and the glass transition temperature was measured 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 ⁻² at a wavelength of 588.8 nm. The Abbe number was 26.0. The total light transmittance was 89%. The results are shown in Table 1.

[Comparative Production Example 1] (Production of Polycarbonate Resin A)
59.0 g (0.13 mol) of bisphenoxyethanolfluorene, 30.0 g (0.14 mol) of diphenyl carbonate, and 55.0 μL (137.5 × 10 ^-8 mol) of a 2.5 × 10 ^-2 mol/L aqueous sodium bicarbonate solution were 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 raised stepwise to 240° C. over 80 minutes, and the pressure was reduced stepwise to 150 mmHg.
The pressure was further reduced stepwise over 40 minutes until a vacuum was reached, and after 20 minutes of holding, 55 g of the resulting polycarbonate resin (hereinafter referred to as "polycarbonate resin A") was taken out. During the reaction, phenol 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.

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

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 (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.

Comparing Comparative Manufacturing Example 1 with Manufacturing Examples 1 to 4, and comparing Comparative Manufacturing Example 1 with Manufacturing Examples 6 and 7, it was found 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.

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

From Production Examples 6 and 7, it was confirmed that the glass transition temperature of the resin increases significantly as the copolymerization ratio of compound 3 increases. Therefore, resins using compound 3 (included in the compounds represented by general formula (1b)) are suitable for high heat resistance applications.

From Production Example 9, it is believed 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 fine-tune 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.

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 the 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 (13)

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.

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group. Ring A represents a benzene ring.] The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1a).

[In the formula, ^R2 represents a hydrogen atom. ^R1 is the same as above.] The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1b).

[In the formula, ^R2 represents a hydrogen atom. ^R1 is the same as above.] The resin modifier according to claim 1, wherein the compound represented by general formula (1) is a compound represented by general formula (1c).

[In the formula, ^R2 represents a hydrogen atom. ^R1 is the same as above.] The resin modifier according to claim 1, wherein the resin is a polycarbonate resin or a polyester carbonate resin. The resin modifier according to claim 1, wherein the resin is a resin used for optical components. The resin modifier according to claim 6, wherein the optical component is an optical lens, an optical film, or an optical sheet. A compound represented by general formula (1a):

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group; and R ² represents a hydrogen atom.] A compound represented by general formula (1c):

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group; and R ² represents a hydrogen atom.] 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).

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group; and R ² represents a hydrogen atom.] 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).

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group; and R ² represents a hydrogen atom.] Use of a compound represented by formula (1) as a raw material monomer for producing a resin having a carbonate bond in the molecule.

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group. Ring A represents a benzene ring.] 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.

[In the formula, R ¹ is the same or different and represents a methyl group or an ethyl group. Ring A represents a benzene ring.]

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