JP5825798B2 - Compound for optical element, optical material and optical element - Google Patents

Description

  The present invention relates to a compound for an optical element, and an optical material and an optical element using the same, and particularly relates to a (meth) acrylate compound having specific optical characteristics, and an optical material and an optical element using the same.

In general, the refractive index of an optical material made of glass material (glass material), organic resin, or the like gradually increases as the wavelength becomes shorter. By the way, as an index representing the wavelength dispersion of the refractive index, there are Abbe number (ν _d ), secondary dispersion characteristic (θg, F), and the like. The Abbe number, θg, and F value are values specific to each optical material, but in many cases are within a certain range. FIG. 1 is a diagram showing the relationship between secondary dispersion characteristics and Abbe number of conventional optical materials (glass material and organic resin).

The Abbe number (ν _d ) and the secondary dispersion characteristic (θg, F) are expressed by the following equations.
Abbe number [ν _d ] = (n _d −1) / (n _F −n _C )
Secondary dispersion characteristic [θg, F] = ( _ng −n _F ) / (n _F −n _C )
(N _d is the refractive index at a wavelength of 587.6 nm, n _F is the refractive index at a wavelength of 486.1 nm, n _C is the refractive index at a wavelength of 656.3 nm, _ng is (The refractive index at a wavelength of 435.8 nm.)

  By the way, by designing the structure (material type and molecular structure) of the optical material (glass material, organic resin, etc.) in detail, it has excellent optical characteristics (high θg, F characteristics) that are out of the predetermined range. Optical materials have also been proposed. For example, polyvinyl carbazole which is an organic resin shown by A in FIG. 1 has higher secondary dispersion characteristics (high θg, F characteristics) than a general-purpose organic resin material.

  In general, in a refractive optical system, it is possible to reduce chromatic aberration by appropriately combining glass materials having different dispersion characteristics. For example, in an objective lens such as a telescope, a chromatic aberration appearing on the axis is corrected by using a glass material having a small dispersion as a positive lens and a glass material having a large dispersion as a negative lens. However, when the configuration and number of lenses are limited, or when the glass material used is limited, it may be very difficult to sufficiently correct chromatic aberration. As one method for solving such a problem, there is a method of using a glass material having anomalous dispersion characteristics, and optical elements are designed using this method.

  In addition, when manufacturing an optical element that has an excellent chromatic aberration correction function and has an aspherical shape or the like, it is better to produce organic resin on a spherical glass or the like than to use a glass material as a material. There is an advantage that it is excellent in performance, freedom of shape, and lightness. However, the optical characteristics of conventional organic resins are within a limited range (secondary dispersion characteristics [θg, F] is 0.700 or less) as shown in FIG. Very few organic resins are shown.

  In the background as described above, Patent Document 1 proposes an optical resin composition in which N-acryloylcarbazole, polyfunctional polyester acrylate, dimethylol tricyclodecane diacrylate, and a polymerization initiator are mixed at a predetermined ratio. Has been. Patent Document 1 reports that the above-described optical resin composition is easy to process and has a material having sufficient anomalous dispersion and durability in a cured product.

Patent Document 2 proposes a heteroaromatic compound containing an aromatic compound in which at least one heterocyclic compound having π electrons is bonded via an sp ₂ carbon atom. . According to Patent Document 2, the proposed heteroaromatic compound has a high refractive index dispersion characteristic (Abbe number (ν _d )) and a high secondary dispersion characteristic (θg, F) (anomalous dispersion characteristic). ), A material having a high characteristic of correcting chromatic aberration.

JP 2008-158361 A JP 2010-202530 A

  However, there is currently no material having practicality (low coloration, high transparency) among the materials having the characteristics (high θg, F characteristics) in the area indicated by B in FIG. All the materials proposed in Patent Document 1 have a θg and F value of 0.70 or less. Furthermore, although the material proposed in Patent Document 2 has a θg, F value of 0.70 or more, the transmittance is low. Specifically, the transmittance of light having a wavelength of 430 nm is 91% or less in a sample having a thickness of 12.5 μm.

The present invention has been made in view of the background art described above, and the object thereof is high in refractive index dispersion characteristics (Abbe number (ν _d )) and secondary dispersion characteristics (θg, F), and is visible. An object of the present invention is to provide a compound for optical materials having a high transmittance in the light region and a high chromatic aberration correction function.

The organic compound for optical materials of the present invention is a compound represented by the following general formula (1) or (2) (excluding 2,2-bis (4-acryloyloxyethoxybiphenyl) sulfone) .)

（式（１）において、Ｘ及びＹは、それぞれ下記に示される置換基から選択される置換基である。

(In Formula (1), X and Y are substituents each selected from the substituent shown below.

（＊は、Ｒ₁又はＲ₂との結合手を表す。）
Ｒ₁及びＲ₂は、それぞれ水素原子、炭素数１乃至２のアルキル基及び（メタ）アクリロイル基から選択される置換基である。Ｚ₁及びＺ₂は、それぞれ水素原子、ハロゲン原子、炭素数１乃至２のアルコキシ基、炭素数１乃至２のアルキルチオ基、置換あるいは無置換の炭素数１乃至２のアルキル基から選択される置換基である。ａ及びｂは、それぞれ０乃至２の整数である。ａが２のとき２つのＺ₁は、同じであってもよいし異なっていてもよい。ｂが２のとき２つのＺ₂は、同じであってもよいし異なっていてもよい。）
（式（２）において、Ｘは、下記に示される置換基から選択される置換基である。

(* Represents a bond with R ₁ or R ₂ )
R ₁ and R ₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group. Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms It is a group. a and b are integers of 0 to 2, respectively. When a is 2, the two Z ₁ may be the same or different. When b is 2, the two Z ₂ may be the same or different. )
(In Formula (2), X is a substituent selected from the substituents shown below.

（＊は、Ｒ₁₁との結合手を表す。）
Ｙは、下記に示される置換基から選択される置換基である。

(* Represents a bond with R ₁₁ )
Y is a substituent selected from the substituents shown below.

（＊は、Ｒ₁又はＲ₂との結合手を表す。）
Ｒ₁及びＲ₂は、それぞれ水素原子、炭素数１乃至２のアルキル基及び（メタ）アクリロイル基から選択される置換基である。Ｚ₁及びＺ₂は、それぞれ水素原子、ハロゲン原子、炭素数１乃至２のアルコキシ基、炭素数１乃至２のアルキルチオ基、無置換の炭素数１乃至２のアルキル基及び下記式（３）に示す置換基から選択される置換基である。

（式（３）において、＊＊は、結合手を表し、ｍは、０又は１であり、ｎは、２乃至４の整数であり、Ｒは、水素又はメチル基である。）
ａ及びｂは、それぞれ０乃至２の整数である。ａが２のとき２つのＺ₁は、同じであってもよいし異なっていてもよい。ｂが２のとき２つのＺ₂は、同じであってもよいし異なっていてもよい。）

(* Represents a bond with R ₁ or R ₂ )
R ₁ and R ₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group. Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an unsubstituted alkyl group having 1 to 2 carbon atoms, and the following formula (3): It is a substituent selected from the substituents shown.

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
a and b are integers of 0 to 2, respectively. When a is 2, the two Z ₁ may be the same or different. When b is 2, the two Z ₂ may be the same or different. )

  According to the present invention, it is possible to provide an organic compound for an optical material having a high refractive index dispersion characteristic (Abbe number (νd)) and secondary dispersion characteristic (θg, F) and a high chromatic aberration correction function. .

  For this reason, the optical element obtained by shaping | molding the optical material which has the organic compound for optical materials of this invention can remove a chromatic aberration efficiently. Therefore, according to the present invention, the optical system can be made lighter and shorter.

It is the graph which showed the relationship between the secondary dispersion characteristic and the Abbe number of the optical material marketed. It is the schematic which shows the example of the optical element of this invention.

  Hereinafter, the present invention will be described in detail.

  First, the organic compound for optical elements of the present invention will be described. The organic compound for optical elements of the present invention is specifically a compound represented by the following general formula (1) or (2).

  The organic compound for an optical element of the present invention is a compound having a partial structure represented by the following (1A) or (2A) as a basic skeleton, preferably a partial structure represented by the following (1A) or (2A) And a (meth) acryloyl group.

（式（１Ａ）及び式（２Ａ）において、Ｘ₀及びＹ₀は、それぞれ酸素原子又は硫黄原子である。）

(In Formula (1A) and Formula (2A), X ₀ and Y ₀ are each an oxygen atom or a sulfur atom.)

  In addition, the preferable aspect of the organic compound for optical elements of this invention is mentioned later.

  First, the compound of formula (1) will be described. In the formula (1), X and Y are each a substituent selected from the substituents shown below.

In the substituent represented by X and Y in the formula (1), * represents a bond with R ₁ or R ₂ .

In the formula (1), R ₁ and R ₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group.

Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group and an ethyl group.

In Formula (1), Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, or a substituted or unsubstituted alkyl having 1 to 2 carbon atoms. A substituent selected from the group.

Examples of the halogen atom represented by Z ₁ and Z ₂ include fluorine, chlorine, bromine and iodine.

Examples of the alkoxy group represented by Z ₁ and Z ₂ include a methoxy group and an ethoxy group.

Examples of the alkylthio group represented by Z ₁ and Z ₂ include a methylthio group and an ethylthio group.

Examples of the alkyl group represented by Z ₁ and Z ₂ include a methyl group and an ethyl group. The alkyl group further includes (meth) acryloyloxy group, (meth) acryloyloxyethoxy group (1- (meth) acryloyloxyethoxy group, 2- (meth) acryloyloxyethoxy group), 2-hydroxyethoxy group. 2-mercaptoethoxy group, 2-mercaptoethylthio group, (meth) acryloyloxypropoxy group (1- (meth) acryloyloxypropoxy group, 2- (meth) acryloyloxypropoxy group, 3- (meth) acryloyloxypropoxy group Group), 3-hydroxypropoxy group, 3-mercaptopropoxy group, 3-mercaptopropylthio group, (meth) acryloyloxybutoxy group (1- (meth) acryloyloxybutoxy group, 2- (meth) acryloyloxybutoxy group, 3- (meth) acrylo Ruoxybutoxy group, 4- (meth) acryloyloxybutoxy group), 4-hydroxybutoxy group, 4-mercaptobutoxy group, 4-mercaptobutylthio group, allyloxy group, allylthio group, 4-vinylbenzyloxy group, oxira It may have a substituent selected from an nylmethoxy group, an oxiranylethoxy group, a thiranylmethoxy group, a thiranylethoxy group, a methylthio group, an ethylthio group, a methoxy group, and an ethoxy group.

In Formula (1), a and b are integers of 0 to 2, respectively. Here, when a is 2, two Z ₁ may be the same or different. When b is 2, the two Z ₂ may be the same or different. In consideration of easiness of synthesis, a and b are preferably 0 or 1, respectively.

  Next, the preferable aspect of the compound shown by Formula (1) is demonstrated. Here, the preferable aspect of the compound shown by Formula (1) is divided roughly into following (1-1) and (1-2).

  (1-1) When X and Y are each a substituent selected from the substituents shown below

（１−２）Ｘ及びＹが、それぞれ硫黄原子（−Ｓ−）又は酸素原子（−Ｏ−）である場合

(1-2) When X and Y are each a sulfur atom (—S—) or an oxygen atom (—O—)

  In the case of (1-1), an embodiment that satisfies the following (1-1-1) to (1-1-3) is more preferable.

  (1-1-1) X and Y are each a substituent selected from the substituents shown below.

（１−１−２）Ｒ₁及びＲ₂が、それぞれ水素原子、炭素数１乃至２のアルキル基及び（メタ）アクリロイル基から選択される置換基であること
（１−１−３）Ｚ₁及びＺ₂が、それぞれ水素原子、ハロゲン原子、炭素数１乃至２のアルコキシ基、炭素数１乃至２のアルキルチオ基、置換あるいは無置換の炭素数１乃至２のアルキル基から選択される置換基であること

(1-1-2) R ₁ and R ₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group (1-1-3) Z _1. And Z ₂ are each a substituent selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. There is

In the case of (1-1), an embodiment that satisfies the above (1-1-1) and the following (1-1-4) and (1-1-5) is particularly preferable.
(1-1-4) R ₁ and R ₂ are each hydrogen or a (meth) acryloyl group (1-1-5) Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, or a carbon number of 1 to 2 a substituent selected from an alkoxy group having 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and an alkyl group having 1 to 2 carbon atoms.

In the case of (1-2), an embodiment satisfying the following (1-2-1) to (1-2-3) is preferable.
(1-2-1) X and Y are each —S— or —O—. (1-2-2) R ₁ and R ₂ are each hydrogen or an alkyl group having 1 to 2 carbon atoms. (1-2-3) Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 2 carbon atoms. A substituent selected from alkyl groups of

In the case of (1-2), an embodiment that satisfies the above (1-2-1) and (1-2-2) and the following (1-2-4) is more preferable.
(1-2-4) Z ₁ and Z ₂ are each a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms.

Furthermore, in the case of (1-2), an embodiment that satisfies the above (1-2-1) and (1-2-4) and the following (1-2-5) is particularly preferable.
(1-2-5) R ₁ and R ₂ are each an alkyl group having 1 to 2 carbon atoms.

Incidentally, when Z ₁ and Z ₂ is an alkyl group having 1 to 2 carbon atoms having a substituent group, the structure as a specific structure of the alkyl group represented by the following general formula (3) is preferable.

In the formula (3), ** represents a bond. M is 0 or 1, and n represents an integer of 2 to 4. Note that m is preferably 0 from the viewpoint of ease of synthesis. Here, when _one of the structures of Z ₁ and Z ₂ is a structure represented by the formula (3), the compound itself becomes a more flexible structure, so that the melting point of the compound itself can be lowered. It can be said that lowering the melting point of the compound itself is advantageous from the viewpoint of ease of molding.

  Next, the compound of the following general formula (2) will be described.

  In Formula (2), X is a substituent selected from the substituents shown below.

In the substituent represented by X in formula (2), * represents a bond to R ₁₁ .

  In Formula (2), Y is a substituent selected from the substituents shown below.

In the substituent represented by Y in formula (2), * represents a bond to R ₁₂ .

In the formula (2), R ₁₁ and R ₁₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group.

Examples of the alkyl group represented by R ₁₁ and R ₁₂ include a methyl group and an ethyl group.

In the formula (2), Z ₃ is selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms. It is a substituent.

Examples of the alkoxy group represented by Z ₃ include a methoxy group and an ethoxy group.

Examples of the alkylthio group represented by Z ₃ include a methylthio group and an ethylthio group.

Examples of the alkyl group represented by Z ₃ include a methyl group and an ethyl group. The alkyl group further includes (meth) acryloyloxy group, (meth) acryloyloxyethoxy group (1- (meth) acryloyloxyethoxy group, 2- (meth) acryloyloxyethoxy group), 2-hydroxyethoxy group. 2-mercaptoethoxy group, 2-mercaptoethylthio group, (meth) acryloyloxypropoxy group (1- (meth) acryloyloxypropoxy group, 2- (meth) acryloyloxypropoxy group, 3- (meth) acryloyloxypropoxy group Group), 3-hydroxypropoxy group, 3-mercaptopropoxy group, 3-mercaptopropylthio group, (meth) acryloyloxybutoxy group (1- (meth) acryloyloxybutoxy group, 2- (meth) acryloyloxybutoxy group, 3- (meth) acrylo Ruoxybutoxy group, 4- (meth) acryloyloxybutoxy group), 4-hydroxybutoxy group, 4-mercaptobutoxy group, 4-mercaptobutylthio group, allyloxy group, allylthio group, 4-vinylbenzyloxy group, oxira It may have a substituent selected from an nylmethoxy group, an oxiranylethoxy group, a thiranylmethoxy group, a thiranylethoxy group, a methylthio group, an ethylthio group, a methoxy group, and an ethoxy group.

In the formula (2), c is an integer of 0 to 2. When c is 2, the two Z ₃ may be the same or different. In consideration of easiness of synthesis, c is preferably 0 or 1.

  Next, the preferable aspect of the compound shown by Formula (2) is demonstrated. Among the compounds represented by the formula (2), a preferable embodiment is an embodiment that satisfies the following (2-1) to (2-4).

  (2-1) X is a substituent selected from the substituents shown below.

（２−２）Ｙが、下記に示される置換基から選択される置換基であること

(2-2) Y is a substituent selected from the substituents shown below.

（２−３）Ｒ₁₁及びＲ₁₂が、それぞれ水素原子、炭素数１乃至２のアルキル基及び（メタ）アクリロイル基から選択される置換基であること
（２−４）Ｚ₃が、水素原子、ハロゲン原子、炭素数１乃至２のアルコキシ基、炭素数１乃至２のアルキルチオ基及び置換あるいは無置換の炭素数１乃至２のアルキル基から選択される置換基であること

(2-3) R ₁₁ and R ₁₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group. (2-4) Z ₃ is a hydrogen atom. , A halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms.

Moreover, a more preferable aspect among the compounds shown by Formula (2) is an aspect which satisfies the said (2-3) and (2-4) and following (2-5) and (2-6).
(2-5) X is a substituent selected from the substituents shown below.

（２−６）Ｙが、下記に示される置換基から選択される置換基であること

(2-6) Y is a substituent selected from the substituents shown below.

Of the compounds represented by formula (2), particularly preferred embodiments are those satisfying the above (2-5) and (2-6) and the following (2-7) and (2-8).
(2-7) R ₁₁ and R ₁₂ are each a substituent selected from a hydrogen atom and a (meth) acryloyl group. (2-8) Z ₃ is a hydrogen atom, a halogen atom, or 1 to 2 carbon atoms. And a substituent selected from an alkoxy group having 1 to 2 carbon atoms and an alkyl group having 1 to 2 carbon atoms

By the way, when Z < ₃ > is a C1-C2 alkyl group which has a substituent, the structure shown by following General formula (3) is preferable as a specific structure of the said alkyl group.

In the formula (3), ** represents a bond. M is 0 or 1, and n represents an integer of 2 to 4. Note that m is preferably 0 from the viewpoint of ease of synthesis. Here, when the structure of Z _{3 is} a structure represented by the formula (3), since the compound itself becomes a more flexible structure, the melting point of the compound itself can be lowered. It can be said that lowering the melting point of the compound itself is advantageous from the viewpoint of ease of molding.

Next, an example is given and demonstrated about the manufacturing method of the organic compound for optical materials which concerns on this invention. The production route of the organic compound for optical materials according to the present invention is not particularly limited, and any production method can be adopted. However, at least the following synthesis steps (a) and (b) are included, and depending on the compound, the synthesis step (c) is further included.
(A) Bond formation between aromatic rings (benzene rings) (b) Ether (thioether) reaction (c) (meth) acrylate reaction

  Considering ease of synthesis and the like, the synthesis process is performed in the order of (a), (b), and (c).

  In the synthesis step (a), it can be changed flexibly depending on the type of functional group of the aromatic compound. For example, a coupling reaction with a transition metal catalyst, an oxidative coupling reaction between halides, a substitution reaction on an aromatic ring, and the like. In view of the reaction yield, a coupling reaction with a transition metal catalyst is desirable.

  The coupling reaction with a transition metal catalyst can be arbitrarily selected. As typical methods, Suzuki coupling using boric acid or the like, Stille coupling using organic tin, Negishi coupling using organic zinc, or the like is preferably used.

  In the synthesis step (b), a typical method for the etherification reaction is a Williamson ether synthesis method in which a hydroxyl group is salted with sodium hydride, potassium hydroxide or the like, and then a corresponding halide is added.

On the other hand, the thioetherification reaction is performed by a thiol group generation reaction and a reaction between a thiol group and a halide. Here, in the thiol group generation reaction, for example, a hydroxyl group is converted into a substituent active for a nucleophilic substitution reaction (TsO—, Cl—, CF ₃ S (═O) ₂ —O—, etc.), This is achieved by performing a nucleophilic substitution reaction using ions (S ²⁻ ). In the reaction between a thiol group and a halide, the above-described Williamson ether synthesis method can be applied.

  In the synthesis step (c), representative methods include esterifying a hydroxyl group using (meth) acrylic acid halide or (meth) acrylic anhydride, and (meth) acrylic acid lower alcohol ester. Transesterification reaction used, direct esterification reaction using (de) condensation of (meth) acrylic acid and the diol using a dehydrating condensing agent such as N, N′-dicyclohexylcarbodiimide, and (meth) acrylic acid and the diol in sulfuric acid A method of heating in the presence of a dehydrating agent such as is preferably used.

  Moreover, when the organic compound for optical materials which concerns on this invention is a (meth) acrylate compound, you may use a polymerization inhibitor as needed so that superposition | polymerization may not advance at the time of reaction or a preservation | save. Examples of polymerization inhibitors include hydroquinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 2,5-diphenylparabenzoquinone, and N-oxy radicals such as tetramethylpiperidinyl-N-oxy radical (TEMPO). , Substituted catechols such as t-butylcatechol, amines such as phenothiazine, diphenylamine and phenyl-β-naphthylamine, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride and the like. Of these, hydroquinones, phenothiazines and N-oxy radicals are preferred from the viewpoint of versatility and polymerization inhibition.

  The lower limit of the amount of the polymerization inhibitor used relative to the (meth) acrylate compound is usually 10 ppm or more, preferably 50 ppm or more, and the upper limit is usually 10,000 ppm or less, preferably 1000 ppm or less. If the amount is too small, the effect as a polymerization inhibitor does not appear or is small, and there is a risk that the polymerization proceeds during the reaction or the concentration in the post-treatment process. This is not preferable because it may become an impurity in the production of, and may have an adverse effect such as inhibiting polymerization reactivity.

  Next, the characteristics of the organic compound for optical elements of the present invention will be described.

In order to provide an optical element with a higher chromatic aberration correction function than in the past, it is extremely effective in terms of optical design to satisfy the following (i) and (ii) as material characteristics of the optical element. I focused on that.
(I) High transmittance in the visible light region (ii) Secondary dispersion characteristics (θg, F) deviate from general-purpose materials and have larger characteristics (high θg, F characteristics)

Specifically, it is an area B shown in FIG. 1 where the relationship between the Abbe number (ν _d ) and the secondary dispersion characteristics (θg, F) is deviated from the plot of the general-purpose material of glass material or organic resin. . Specifically, the internal transmittance of 500 μm is a characteristic of 90% or more at 410 nm. Here, the characteristics of the B area are ν _d <25, θg, F> 0.70.

As a result of intensive studies on materials satisfying the characteristics of the B area shown in FIG. 1, the present inventors have a long conjugated structure having at least one electron-withdrawing substituent capable of conjugation and one electron-donating substituent. Aromatic compounds have high refractive index dispersion characteristics (Abbe number (ν _d )), high secondary dispersion characteristics (θg, F) (high θg, F characteristics), high chromatic aberration correction function and practicality It has been found that it becomes a material that combines. That is, the present inventors have found a compound having the basic structure as a partial structure represented by the following (1A) or (2A).

  In general, a compound having a long conjugated structure typified by an aromatic compound has a smaller band gap than that of a general-purpose material, and thus the absorption edge in the ultraviolet region is shifted to the visible light region side. Due to the influence, a compound having a long conjugated structure has a high refractive index characteristic. Since this high refractive index characteristic has an influence on the short wavelength side, the secondary dispersion characteristics (θg, F) are inevitably increased so that the characteristics of the compound fall within the area B shown in FIG. However, a practical material cannot be obtained by simply connecting aromatic compounds to construct a long conjugated structure. For example, large aromatic compounds still have problems in terms of synthesis, compatibility with other compounds, and coloring. Therefore, an aromatic compound having a long conjugated structure having at least one electron-withdrawing substituent capable of conjugation and one electron-donating substituent is desirable.

  Thus, from the viewpoint of increasing the refractive index characteristics and the secondary dispersion characteristics, the longer the conjugate length of the compound, the better. However, if the conjugated structure becomes too long, the transmittance on the short wavelength side of the visible light region is lowered. Therefore, when considering the use as an optical material, it is necessary to adjust the length of the conjugated structure. Here, in the partial structures represented by the general formulas (1A) and (2A), the salt and plum have a conjugate length enough for the transmittance and the refractive index characteristics.

  By the way, examples of the electron-withdrawing substituent that can be conjugated include sulfone, ketone, imine, oxime, nitrile, nitro, and ester. In consideration of the long-term stability of the product, sulfone, ketone, nitrile and ester are preferable, and sulfone is more preferable. For this reason, the organic compound for optical elements of the present invention is a compound having a sulfone as a partial structure as shown in (1A) and (2A).

  Examples of the electron-donating substituent that can be conjugated include a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an alkyl group, an amino group, an alkylamino group, a dialkylamino group, and a carbonyloxy group. Preferred are a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an alkyl group, and a carbonyloxy group. However, if the molecular weight of the substituent becomes too large, high secondary dispersion characteristics (θg, F) cannot be obtained. Therefore, the substituent is preferably a substituent having 0 to 10 carbon atoms. From the viewpoint of easy synthesis, a substituent having 1 to 4 carbon atoms is preferable. In the present invention, particularly preferred substituents are a hydroxyl group, a mercapto group, an alkoxy group having 1 to 4 carbon atoms, and an alkylthio group having 1 to 4 carbon atoms.

  In addition, H (hydrogen atom) shown in the formulas (1) and (2) is necessary for adjusting the conjugated structure, and in other substituents, aromatic rings due to steric hindrance of the substituent Conjugation may occur due to twisting of the material, and the characteristics may not be exhibited.

  Next, the optical material according to the present invention will be described.

The optical material of the present invention is roughly classified into the following (A) to (C).
(A) Material obtained by containing the organic compound for optical material of the present invention in a matrix polymer (B) Material obtained by polymerizing the organic compound for optical material of the present invention (C) Organic compound for optical material of the present invention and others A material obtained by copolymerizing a compound of

  Here, among the organic compounds for optical materials of the present invention, a compound having no (meth) acryloyl group is used in the form of (A). On the other hand, among the organic compounds for optical materials of the present invention, the compound having a (meth) acryloyl group can be used in any of the forms (A) to (C), but exclusively (B) or ( C).

  When the organic compound for an optical material of the present invention is used in the form of (A), as a matrix polymer, a (meth) acrylic polymer; an allyl polymer; an ethylene homopolymer, ethylene and propylene, 1-butene, 1-pentene, Random or block copolymer of 1-hexene, 4-methyl-1-pentene or one or more α-olefins, ethylene and vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate 1 type or 2 or more types of random or block copolymers, 1 type of propylene homopolymer, 1-butene other than propylene and propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc. Random or block copolymer with two or more α-olefins, 1-butene homopolymer, ionomer resin, Further, polyolefin resins such as a mixture of these polymers; hydrocarbon atom resins such as petroleum resins and terpene resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; nylon 6, nylon 66, nylon 11 , Nylon 12, nylon 610, nylon 6/66, nylon 66/610, nylon MXD and other polyamide resins; polymethyl methacrylate and other acrylic resins; polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer Styrene, acrylonitrile resin such as polyacrylonitrile; polyvinyl alcohol resin such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polycarbonate resin; ; Polymethylene oxide resins; polysulfone resins; polyimide resin; polyamideimide resins. The (meth) acrylic polymer is a polymer obtained by polymerizing a (meth) acrylate compound described later. The allyl polymer is a polymer obtained by polymerizing an allyl compound described later. These resins may be used alone or in combination of two or more. These matrix polymers are appropriately selected in consideration of compatibility with the organic compound for optical materials of the present invention.

  When the organic compound for optical material of the present invention is used in the form (A), the content of the organic compound for optical material of the present invention relative to the whole material is compatible with the organic compound for optical material of the present invention and the matrix polymer. Is selected as appropriate.

  When the organic compound for optical material of the present invention is used in the form of (A), the content of the resin to be the matrix polymer is 50% by weight or more and 99% by weight or less based on the whole material. Considering the θg, F characteristics of the obtained optical material and the brittleness of the molded product, it is preferably 50% by weight or more and 80% by weight or less.

  When the organic compound for optical material of the present invention is used in the form (B), the optical material of the present invention is a composition comprising the organic compound for optical material of the present invention ((meth) acrylate compound) and a polymerization initiator. Made from things. The composition may further contain a polymerization inhibitor, a photosensitizer, a resin and the like as necessary.

  Examples of the polymerization initiator include, but are not limited to, those that generate radical species by irradiation with light, those that generate cationic species, and those that generate radical species by heat.

  As a polymerization initiator that generates radical species by light irradiation, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy- 2-methyl-1-phenyl-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4′-diphenylbenzophenone, 4 , 4'-diphenoxybenzophenone and the like, but not limited thereto.

  As a polymerization initiator that generates a cationic species by light irradiation, iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate is exemplified as a suitable polymerization initiator. It is not limited to.

  Furthermore, examples of polymerization initiators that generate radical species by heat include azo compounds such as azobisisobutyl nitrile (AIBN), benzoyl peroxide, t-butyl peroxypivalate, t-butyl peroxyneohexanoate, t -Peroxides such as hexyl peroxyneohexanoate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, cumylperoxyneohexanoate, cumylperoxyneodecanoate Although it is mentioned, it is not limited to these.

  In the optical material of the present invention, when the organic compound for optical material of the present invention is used in the form of (B), the content of the organic compound for optical material of the present invention is desirably 1.0 wt% or more and 99 wt% or less. It is preferably 50% by weight or more and 99% by weight or less.

  In the optical material of the present invention, when the organic compound for optical material of the present invention is used in the form of (B), the addition amount of the photopolymerization initiator used for curing and molding of the optical material of the present invention is based on the polymerizable component. On the other hand, the range of 0.01% by weight or more and 10.00% by weight or less is preferable. In addition, a photoinitiator can also be used only by 1 type according to the reactivity of resin, and the wavelength of light irradiation, and can also be used in combination of 2 or more types.

  In the optical material of the present invention, when the organic compound for optical material of the present invention is used in the form of (B), the polymerization inhibitor used as the preservative of the organic compound for optical material of the present invention is the polymerization prohibition described above. Agents.

  In the case of initiating polymerization by irradiating ultraviolet rays or the like as light, a known sensitizer can also be used. Typical sensitizers include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin Examples include isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and acylphosphine oxide.

  The addition ratio of the photopolymerization initiator to the polymerizable resin component can be appropriately selected according to the amount of light irradiation and further the additional heating temperature. Moreover, it can also adjust according to the average molecular weight made into the target of the polymer obtained.

  The addition amount of the photopolymerization initiator used for curing / molding the optical material of the present invention is preferably in the range of 0.01 wt% to 10.00 wt% with respect to the polymerizable component. The photopolymerization initiator can be used alone or in combination of two or more depending on the reactivity of the resin and the wavelength of light irradiation.

  When using the organic compound for optical materials of this invention with the form of (C), there is no restriction | limiting in particular as a compound copolymerized with the organic compound for optical materials of this invention. For example, 1,3-adamantanediol dimethacrylate, 1,3-adamantane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, propoxylated neopentyl glycol diacrylate, dipropylene glycol diacrylate, ethoxylated Bisphenol A dimethacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isobornyl acrylate, iso Bonyl methacrylate, 1,3-butylene glycol diacrylate, 1,4-butanedioldia Relate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 9,9-bis [4- (2 -Acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-me Acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-acryloyloxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxy) phenyl] fluorene, benzyl acrylate, benzyl methacrylate , Butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene Glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, Ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) Propane, 2,2-bis (4-acryloxydiethoxyphene) Propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, 1,1-bis (4- Acryloxyethoxyphenyl) sulfone, 1,1-bis (4-methacryloxyethoxyphenyl) sulfone, 1,1-bis (4-acryloxydiethoxyphenyl) sulfone, 1,1-bis (4-methacryloxydiethoxy) Phenyl) sulfone, dimethylol tricyclodecane diacrylate, trime Roll propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylene diene (Meth) acrylate compounds such as thiol diacrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, die Examples include allyl compounds such as tylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3,9-divinylspirobi (m-dioxane), and diisopropenylbenzene. . However, the present invention is not limited to these.

  When the organic compound for optical material of the present invention is used in the form of (C), the content of the compound to be copolymerized with the organic compound for optical material of the present invention is 1.0% by weight or more and 80% by weight based on the whole material. It is as follows. Considering the θg, F characteristics of the obtained optical material and the brittleness of the molded product, it is preferably 1.0% by weight or more and 30% by weight or less.

  Next, the optical element of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the optical element of the present invention. In the optical element (a), a thin film (optical member 10) formed by molding the optical material of the present invention is provided on one surface of the lens substrate 20. As a method of manufacturing the optical element in FIG. 1A, for example, a method of forming a thin layer structure on a substrate made of a light transmissive material is employed. Specifically, a mold made of a metal material is provided at a certain distance from the glass substrate, and a gap between the mold and the glass substrate is filled with a flowable optical material or optical resin composition. Molding is performed by holding lightly. Then, if necessary, the optical material or the optical resin composition is polymerized while being kept in that state. The light irradiation used for such a polymerization reaction is performed using light of a suitable wavelength, usually ultraviolet light or visible light, corresponding to the mechanism resulting from radical generation using a photopolymerization initiator. For example, light irradiation is uniformly performed on a light-transmitting material used as the substrate, specifically, a raw material such as a monomer for preparing an optical material that is molded through a glass substrate. The amount of light to be irradiated is appropriately selected according to the mechanism resulting from radical generation using the photopolymerization initiator and according to the content ratio of the contained photopolymerization initiator.

  On the other hand, in the production of a molded body of an optical material by such a photopolymerization reaction, it is more preferable that the irradiated light is uniformly irradiated to the entire raw material such as a monomer that is molded. Therefore, it is more preferable to select light having a wavelength that can be uniformly applied through a light-transmitting material used for the substrate, for example, a glass substrate. At this time, it is more suitable for the present invention to reduce the thickness of the molded body of the optical material formed on the substrate of the light transmissive material.

  On the other hand, in the optical element of FIG. 1B, a thin film (optical member 10) formed by molding the optical material of the present invention is provided between the lens substrate 30 and the lens substrate 40. As a method for producing the optical element in FIG. 1B, for example, a similar uncured resin composition or the like between the surface of the molded product on the resin composition side described above and another corresponding lens is used. Is formed by pouring and lightly holding. Then, photopolymerization of the uncured resin composition is performed while maintaining this state. Thereby, a molded body in which the optical material is sandwiched between lenses can be obtained.

  Similarly, a molded body can be produced by a thermal polymerization method. In this case, it is desirable to make the entire temperature more uniform, and it is more suitable for the present invention to reduce the total thickness of the molded body of the polymerizable composition formed on the substrate of the light transmissive material. Become. Further, when the total thickness of the molded body of the optical material to be formed is increased, it is necessary to select the irradiation amount, the irradiation intensity, the light source, etc. in consideration of the film thickness, the absorption of the resin component, the absorption of the fine particle component.

  On the other hand, when forming a molded body of an optical material containing the organic compound for optical material of the present invention, the molding method is not particularly limited, but characteristics such as low birefringence, mechanical strength and dimensional accuracy are included. In order to obtain an excellent molded product, melt molding is particularly preferable. Examples of the melt molding method include press molding, extrusion molding, and injection molding, and injection molding is preferable from the viewpoint of moldability and productivity. The molding conditions in the molding step are appropriately selected depending on the purpose of use or the molding method, but the temperature of the resin composition in the injection molding is preferably in the range of 150 ° C. to 400 ° C., preferably 200 ° C. to 350 ° C. The range is more preferable, and the range of 200 ° C. to 330 ° C. is particularly preferable. By molding in the above temperature range, the resin is imparted with appropriate fluidity during molding to prevent the occurrence of silver streaks due to thermal decomposition of the resin, as well as the occurrence of sink marks and distortion of the molded product. Yellowing can be effectively prevented.

  A molded body obtained by molding the optical material of the present invention by the above molding method can be used as an optical element. Examples of the use of the optical element include a camera lens.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the Example demonstrated below, unless the summary is exceeded. The abbreviations in the reaction formula are as follows. The molecular structure of the synthesized compound was analyzed using JEOL JNM-ECA400 NMR.
THF: tetrahydrofuran DMF: N, N-dimethylformamide TsOH: p-toluenesulfonic acid hydrate

  Synthesis Example 1 Synthesis of 4,4′-bis (4-hydroxyphenyl) diphenylsulfone

The following reagents and solvents were charged into the reaction vessel.
4,4'-dichlorodiphenyl sulfone: 15 g
4-hydroxyphenylboronic acid: 21 g
Sodium bicarbonate: 33g
1,4-dioxane: 500 ml
Water: 250ml
Tetrakistriphenylphosphine palladium: 2.5 g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the degree of reaction progress was confirmed by thin phase chromatography (hereinafter TLC) as needed. After completion of the reaction, the reaction solution was diluted with water, and the organic phase was recovered by solvent extraction. Next, the organic layer was washed with water and then saturated brine, and then dried over anhydrous magnesium sulfate. Next, the residue obtained by concentrating the organic phase under reduced pressure is recrystallized and purified with a mixed solution of hexane and ethyl acetate, whereby 4,4′-bis (4-hydroxyphenyl) diphenylsulfone of pale yellow crystals is obtained. 20 g (yield 95%) of (hereinafter referred to as intermediate compound D1) was obtained.

  Synthesis Example 2 Synthesis of 4- (2-tetrahydropyranyloxyethylthio) -phenylboronic acid pinacol ester

(1) Reagents and solvents shown below were charged into the reaction vessel.
Sodium hydride (55%): 6.2 g
N, N-dimethylformamide: 200 ml

  Next, after cooling the reaction solution to 0 ° C., 25 g of 4-bromothiophenol was slowly added. Next, the reaction solution was stirred while raising the temperature to room temperature. Next, 24 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran was added, the reaction solution was heated to 40 ° C., and stirred at this temperature (40 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then quenched with water and the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, 44 g of 4- (2-tetrahydropyranyloxyethylthio) -bromobenzene was obtained by purifying the crude product obtained by concentrating the organic layer under reduced pressure by column chromatography. The obtained compound was used in the next step as it was.

  (2) The compound obtained in (1) and 400 ml of tetrahydrofuran were put into a reaction vessel. Next, after cooling the reaction solution to −78 ° C., 64 ml of butyl lithium (2.6M) was slowly added dropwise. Next, the reaction solution was further stirred at the same temperature (−78 ° C.) for 2 hours. Next, 35 ml of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise, and the reaction solution was stirred for 12 hours while slowly warming to room temperature. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain 4- (2-tetrahydropyranyloxyethylthio) -phenylboronic acid pinacol ester (hereinafter, intermediate). Body compound D2) (31 g, yield 64%).

  Synthesis Example 3 Synthesis of 4- (4-hydroxyphenylsulfonyl) phenyl trifluoromethanesulfonate

The following reagents and solvents were charged into the reaction vessel.
4,4'-dihydroxydiphenyl sulfone: 25 g
Trifluoromethanesulfonyl chloride: 12ml
Chloroform: 200ml

  Next, after cooling the reaction solution to 0 ° C., 15 ml of triethylamine was slowly added dropwise. Next, the reaction solution was stirred at the same temperature (0 ° C.) for 1 hour. Next, the reaction solution was warmed to room temperature and stirred for another 5 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then stopped with aqueous ammonium chloride solution and the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, 17 g of 4- (4-hydroxyphenylsulfonyl) phenyl trifluoromethanesulfonate (hereinafter referred to as intermediate compound D3) is obtained by purifying the crude product obtained by concentrating the organic layer under reduced pressure by column chromatography. (Yield 45%).

  Synthesis Example 4 Synthesis of 4,4′-bis (3-hydroxymethyl-4-methoxyphenyl) diphenylsulfone

(1) Reagents and solvents shown below were charged into the reaction vessel.
4,4'-dihydroxydiphenyl sulfone: 25 g
Trifluoromethanesulfonyl chloride: 25ml
Chloroform: 300ml

  Next, after cooling the reaction solution to 0 ° C., 42 ml of triethylamine was slowly added dropwise. Next, the reaction solution was stirred at the same temperature (0 ° C.) for 1 hour. Next, the reaction solution was warmed to room temperature and stirred for another 5 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then stopped with aqueous ammonium chloride solution and the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic phase under reduced pressure was recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain 49 g of diphenylsulfone-4,4′-diylbis (trifluoromethanesulfonate) ( Yield 94%). The compound obtained here was used in the next step as it was.

(2) Reagents and solvents shown below were charged into the reaction vessel.
Diphenylsulfone-4,4′-diylbis (trifluoromethanesulfonate) (using the one synthesized in (1) as it is): 28 g
3-formyl-4-methoxyphenylboronic acid: 25 g
Sodium bicarbonate: 30g
Tetrakistriphenylphosphine palladium: 1.3 g
1,4-dioxane: 500 ml
Water: 250ml

  The reaction solution was then heated to 80 ° C. and stirred at this temperature (80 ° C.) for 3 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, 250 ml of water was added, and the reaction solution was stirred at 80 ° C. for 1 hour. Next, the produced crystal (crude crystal) was filtered and collected, and the crude crystal was washed with ethanol and then recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain a light gray crystal.

Next, the obtained light gray crystal and the solvent shown below were charged into the reaction vessel.
Methanol: 200ml
Tetrahydrofuran: 200ml

  Next, after cooling the reaction solution to 0 ° C., 12 g of sodium borohydride was slowly added. Next, the reaction solution was stirred at the same temperature (0 ° C.) while checking the degree of reaction progress by TLC. After confirming the progress of the reaction, 2N hydrochloric acid aqueous solution was added. Next, the reaction solution was stirred at room temperature for 1 hour. Next, the produced | generated crystal | crystallization was wash | cleaned in order of sodium hydrogencarbonate aqueous solution and water. Next, 48 g of 4,4′-bis (3-hydroxymethyl-4-methoxyphenyl) diphenylsulfone (hereinafter referred to as intermediate compound D4) is obtained by recrystallization purification using a mixed solvent of ethanol / ethyl acetate / hexane. (Yield 90%).

[Example 1]
A synthesis scheme of the compound synthesized in Example 1 is shown below. A specific synthesis method will be described below.

(1) Reagents and solvents shown below were charged into the reaction vessel.
Sodium hydride (55%): 620 mg
N, N-dimethylformamide: 30 ml

  Next, the reaction solution was cooled to 0 ° C., and then intermediate compound D1 (2.3 g) was slowly added. Next, the reaction solution was stirred while warming to room temperature. Next, 2.7 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran was added, and then the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then quenched with water and the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the organic phase was concentrated under reduced pressure to obtain a crude product. The crude product thus obtained was used as such in the next step.

(2) The crude product obtained in (1) and the reagents and solvents shown below were charged into a reaction vessel.
Tetrahydrofuran: 10ml
Methanol: 40ml
Paratoluenesulfonic acid hydrate: small amount

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, the produced precipitate is filtered, and then this precipitate is recrystallized and purified with a chloroform / hexane mixed solution to obtain 4,4′-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone 2. 0.3 g (82% yield) was obtained.

(3) Reagents and solvents shown below were charged into the reaction vessel.
4,4′-bis (4- (2-hydroxyethoxy) phenyl) diphenyl sulfone: 3.0 g
Methacrylic acid: 30ml
Paratoluenesulfonic acid: 0.2 g
4-methoxyphenol: 0.2 g
Toluene: 30ml

  Next, the reaction solution was heated and stirred for 20 hours. In addition, the water | moisture content produced | generated at this time was removed suitably, and reaction progress was confirmed at any time by TLC. Next, an aqueous sodium hydroxide solution was added to neutralize the reaction solution, and then the organic phase was extracted with chloroform. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain 2.1 g of 4,4′-bis (4- (2-methacryloyloxyethoxy) phenyl) diphenylsulfone. (Yield 55%).

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.95 (s, 6H), 4.27 (t, 4H), 4.52 (t, 4H), 5.59 (s, 2H), 6. 14 (s, 2H), 6.99-7.01 (m, 4H), 7.25-7.26 (m, 4H), 7.50-7.53 (m, 4H), 7.65- 7.67 (m, 4H), 7.98-8.02 (m, 4H)

[Example 2]
A synthesis scheme of the compound synthesized in Example 2 is shown below. A specific synthesis method will be described below.

(1) Reagents and solvents shown below were charged into the reaction vessel.
Intermediate compound D3: 5 g
Intermediate compound D2: 6 g
Sodium bicarbonate: 4g
Dioxane: 150ml
Water: 70ml
Tetrakistriphenylphosphine palladium: 0.3g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The compound obtained by this purification was directly used in the next step.

(2) Next, the following reagents and solvent were charged into the reaction vessel.
Sodium hydride: 0.6g
N, N-dimethylformamide: 100 ml

  Next, after the reaction solution was cooled to 0 ° C., the compound obtained in (1) was slowly added. Next, the reaction solution was stirred for 2 hours while warming to room temperature. Next, after adding 2.4 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran, the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 10 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the organic layer was concentrated under reduced pressure to obtain a crude product. The obtained crude product was used in the next step as it was.

(3) The crude product obtained in (2) and the reagents and solvents shown below were charged into a reaction vessel.
Tetrahydrofuran: 10ml
Methanol: 40ml
P-Toluenesulfonic acid: small amount

  Next, the reaction solution was stirred at room temperature for 10 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, the produced precipitate is filtered and collected, and recrystallized and purified with a mixed solvent of chloroform / hexane to give 4- (4- (2-hydroxyethylthio) phenyl) -4 ′-(2-hydroxyethyl). 4.1 g (73% yield) of oxy) diphenylsulfone was obtained.

  (4) In Example 1 (3), 4- (4- (2-hydroxyethylthio) phenyl) -4 ′ instead of 4,4′-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone -(2-Hydroxyethyloxy) diphenylsulfone was used. Except for this, synthesis was carried out in the same manner as in Example 1 (3), and 4- (4- (2-methacryloyloxyethylthio) phenyl) -4 ′-(2-methacryloyloxyethyloxy) diphenylsulfone was obtained. 2.5 g (yield 63%) was obtained. In this example, the amount of methacrylic acid used is 20 ml.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.92 (s, 3H), 1.95 (s, 3H), 3.22 (t, 2H), 4.25 (t, 2H), 4. 27 (t, 2H), 4.50 (t, 2H), 5.57 (d, 1H), 5.58 (d, 1H), 6.12 (d, 1H), 6.12 (d, 1H) ), 6.94-7.03 (m, 4H), 7.47-7.67 (m, 4H), 7.89-7.99 (m, 4H)

[Example 3]
A synthesis scheme of the compound synthesized in Example 3 is shown below. A specific synthesis method will be described below.

(1) Reagents and solvents shown below were charged into the reaction vessel.
4,4′-dichlorodiphenyl sulfone: 10 g
4-hydroxyphenylboronic acid: 5.8 g
Sodium bicarbonate: 10g
Dioxane: 400ml
Water: 200ml
Tetrakistriphenylphosphine palladium: 0.8g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 10 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The product thus obtained was used as such in the next step.

(2) Reagents and solvents shown below were charged into the reaction vessel.
Sodium hydride: 1.4g
N, N-dimethylformamide: 200 ml

  Next, after the reaction solution was cooled to 0 ° C., the product obtained in (1) was slowly added. Next, the reaction solution was stirred for 2 hours while warming to room temperature. Next, after adding 6.4 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran, the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 5 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The product thus obtained was used as such in the next step.

(3) The product obtained in (2) and the reagents and solvents shown below were charged into the reaction vessel.
Intermediate compound D2: 6.6 g
Sodium bicarbonate: 4.5g
Dioxane: 300ml
Water: 150ml
Tetrakistriphenylphosphine palladium: 0.3g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The product thus obtained was used as such in the next step.

(4) The product obtained in (3) and the reagents and solvents shown below were charged into the reaction vessel.
Tetrahydrofuran: 10ml
Methanol: 40ml
P-Toluenesulfonic acid: small amount

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, the produced precipitate was filtered and collected, and then the precipitate was recrystallized and purified with a mixed solvent of chloroform / hexane to give 4- (4- (2-hydroxyethylthio) phenyl) -4′-. 5 g (28%) of (4- (2-hydroxyethyloxy) phenyl) diphenylsulfone was obtained.

  (5) In Example 1 (3), 4- (4- (2-hydroxyethylthio) phenyl) -4 ′ instead of 4,4′-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone -(4- (2-Hydroxyethyloxy) phenyl) diphenylsulfone (2.0 g) was used. Except for this, the synthesis was carried out in the same manner as in Example 1 (3), and 4- (4- (2-methacryloyloxyethylthio) phenyl) -4 ′-(4- (2-methacryloyloxyethyloxy) was obtained. ) Phenyl) diphenylsulfone 0.8g (yield 31%) was obtained. In this example, the amount of methacrylic acid used is 20 ml.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.91 (s, 3H), 1.95 (s, 3H), 3.24 (t, 2H), 4.27 (t, 2H), 4. 35 (t, 2H), 4.52 (t, 2H), 5.56-5.60 (m, 2H), 6.09-6.13 (m, 2H), 6.98-7.02 ( m, 2H), 7.45-7.69 (m, 12H), 7.98-8.02 (m, 2H)

[Example 4]
A synthesis scheme of the compound synthesized in Example 4 is shown below. A specific synthesis method will be described below.

(1) Reagents and solvents shown below were charged into the reaction vessel.
4,4′-dichlorodiphenyl sulfone: 13 g
Intermediate compound D2: 50 g
Sodium bicarbonate: 29g
Dioxane: 400ml
Water: 200ml
Tetrakistriphenylphosphine palladium: 2.1 g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after stopping the reaction with an aqueous ammonium chloride solution, the organic phase was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The product thus obtained was used as such in the next step.

(2) The product obtained in (1) and the reagents and solvents shown below were charged into the reaction vessel.
Tetrahydrofuran: 30ml
Methanol: 100ml
P-Toluenesulfonic acid: small amount

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after the produced precipitate was filtered and collected, 19 g of 4,4′-bis (4- (2-hydroxyethylthio) phenyl) diphenylsulfone was obtained by recrystallization purification with a chloroform / hexane mixed solvent. (Yield 74%).

  (3) In Example 1 (3), instead of 4,4′-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone, 4,4′-bis (4- (2-hydroxyethylthio) Phenyl) diphenylsulfone was used. Except for this, synthesis was carried out in the same manner as in Example 1 (3), and 3.0 g (yield 80) of 4,4′-bis (4- (2-methacryloyloxyethylthio) phenyl) diphenylsulfone was obtained. %)Obtained. In this example, the amounts of methacrylic acid and toluene used are 29 ml and 40 ml, respectively.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.91 (s, 6H), 3.22 (t, 4H), 4.35 (t, 4H), 5.56 (s, 2H), 6. 07 (s, 2H), 7.42-7.52 (m, 8H), 7.65-7.71 (m, 4H), 8.00-8.05 (m, 4H)

[Example 5]
A synthesis scheme of the compound synthesized in Example 5 is shown below. A specific synthesis method will be described below.

(1) Reagents and solvents shown below were charged into the reaction vessel.
Sodium hydride (55%): 2.5 g
N, N-dimethylformamide: 200 ml

  Next, the reaction solution was cooled to 0 ° C., and then intermediate compound D1 (10 g) was slowly added. Next, the reaction solution was stirred while warming to room temperature. Next, after adding 5.4 ml of 3-bromopropanol, the reaction solution was heated to 50 ° C. and stirred at this temperature (50 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then quenched with water and the organic phase was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic phase under reduced pressure was recrystallized with a mixed solvent of hexane / ethyl acetate to obtain white crystals. The white crystals thus obtained were used as such in the next step.

  (2) In Example 1 (3), the white crystals obtained in (1) of this example were used in place of 4,4'-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone. Except this, 11.5 g (yield 71%) of 4,4′-bis (4- (3-methacryloyloxypropoxy) phenyl) diphenylsulfone was obtained in the same manner as in Example 1 (3). . In this example, the amounts of methacrylic acid, paratoluenesulfonic acid, methoxyphenol and toluene used are 90 ml, 0.6 g, 0.6 g and 90 ml, respectively.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.94 (s, 6H), 2.19 (dt, 4H), 4.11 (t, 4H), 4.36 (t, 4H), 5. 56 (br, 2H), 6.11 (br, 2H), 6.94-6.99 (m, 4H), 7.45-7.54 (m, 4H), 7.63-7.69 ( m, 4H), 7.96-8.03 (m, 4H)

[Example 6]
A synthesis scheme of the compound synthesized in Example 6 is shown below. A specific synthesis method will be described below.

(1) The following reagents and solvents were charged into the reaction vessel.
4,4′-dichlorodiphenyl sulfone: 10 g
3-methoxy-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol: 25 g
Sodium bicarbonate: 25g
1,4-dioxane: 500 ml
Water: 250ml
Tetrakistriphenylphosphine palladium: 2.5 g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after diluting the reaction solution with water and recovering the organic phase by solvent extraction, the organic layer was washed with water and saturated brine in this order. Next, this organic phase was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. Next, this crude product was recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain 4,4'-bis (4-hydroxy-3-methoxyphenyl) diphenylsulfone as pale yellow crystals. The pale yellow crystals thus obtained were used as such in the next step.

(2) The following reagents and solvents were charged into the reaction vessel.
Sodium hydride (55%): 5.1 g
N, N-dimethylformamide: 300 ml

  Next, the pale yellow crystals obtained in (1) were slowly added to the reaction solution. Next, the reaction solution was stirred at room temperature for 1 hour. Next, 10 ml of 3-bromopropanol was slowly added dropwise, and then the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. The reaction was then quenched with water and the organic phase was extracted with ethyl acetate. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was recrystallized with a mixed solvent of hexane / ethyl acetate to obtain white crystals. The white crystals thus obtained were used as such in the next step.

  (3) In Example 1 (3), white crystals obtained in (2) of this example were used instead of 4,4'-bis (4- (2-hydroxyethoxy) phenyl) diphenylsulfone. Except for this, 21 g (yield 84%) of 4,4′-bis (4- (3-methacryloyloxypropoxy) -3-methoxyphenyl) diphenylsulfone was obtained in the same manner as in Example 1 (3). Obtained. In this example, the amounts used of methacrylic acid, paratoluenesulfonic acid, methoxyphenol and toluene are 120 ml, 1.3 g, 11.3 g and 300 ml, respectively.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.94 (s, 6H), 2.24 (dt, 4H), 3.91 (s, 6H), 4.17 (t, 4H), 4. 37 (t, 4H), 5.56 (br, 2H), 6.11 (br, 2H), 6.92-7.15 (m, 6H), 7.64-7.70 (m, 4H) 7.97-8.03 (m, 4H)

[Example 7]
A synthesis scheme of the compound synthesized in Example 7 is shown below. A specific synthesis method will be described below.

  (1) Instead of 2-methoxy-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol in Example 6 (1), 2,6-dimethyl Synthesis was performed in the same manner as in Example 6 (1) except that -4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenol was used. In this example, the amounts of 4,4'-dichlorodiphenylsulfone and tetrakistriphenylphosphine palladium used are 9.6 g and 2.3 g, respectively. As a result, 4,4'-bis (4-hydroxy-3,5-dimethylphenyl) diphenylsulfone was obtained as white crystals. The white crystals thus obtained were used as such in the next step.

(2) The following reagents and solvents were charged into the reaction vessel.
Sodium hydride (55%): 3.1 g
N, N-dimethylformamide: 300 ml

  Next, the white crystals obtained in (1) were slowly added to the reaction solution, and then the reaction solution was stirred at room temperature for 1 hour. Next, 15 g of 2-bromoethyl methacrylate was slowly added dropwise, and then the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, water was added to stop the reaction, and the organic layer was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain 4,4′-bis (4- (2-methacryloyloxyethoxy) -3,5-dimethylphenyl) diphenyl. 15 g (yield 66%) of sulfone was obtained.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.89 (s, 6H), 2.30 (s, 12H), 4.30 (t, 4H), 4.62 (s, 4H), 5. 47 (br, 2H), 6.05 (br, 2H), 7.21-7.27 (m, 4H), 7.60-7.67 (m, 4H), 7.93-8.01 ( m, 4H)

[Example 8]
A synthesis scheme of the compound synthesized in Example 8 is shown below. A specific synthesis method will be described below.

(1) The following reagents and solvents were charged into the reaction vessel.
Sodium hydride (55%): 11 g
N, N-dimethylformamide: 300 ml solution

  Next, the reaction solution was cooled to 0 ° C., and then intermediate compound D4 (30 g) was slowly added. Next, the reaction solution was stirred at the same temperature (0 ° C.) for 1 hour. Next, after adding 36 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran, the reaction solution was heated to 70 ° C. and stirred at this temperature (70 ° C.) for 6 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, water was added to stop the reaction, and the organic layer was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain a pale yellow liquid. The pale yellow solid thus obtained was used as such in the next step.

(2) The light yellow liquid obtained in (1) and the reagents and solvents shown below were charged into the reaction vessel.
Methanol: 150ml
Tetrahydrofuran: 50ml
P-Toluenesulfonic acid: catalyst amount

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after adding triethylamine to stop the reaction, the produced crystals were filtered and collected. Next, the obtained crystals were recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain white crystals. The white solid thus obtained was used as such in the next step.

(3) The white liquid obtained in (2) and the reagents and solvents shown below were charged into the reaction vessel.
Chloroform: 100ml
Pyridine: 150ml
4-methoxyphenol: 0.2 g
N, N-dimethylaminopyridine: 1.2 g
Methacrylic anhydride: 30 ml

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, 2N hydrochloric acid was added to stop the reaction, and then the organic layer was extracted with toluene. Next, the obtained organic layer was washed with 2N hydrochloric acid, 10% aqueous sodium hydroxide, water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain an oily product. Next, the obtained oily product was recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain 4,4′-bis ((3- (2-methacryloyloxyethoxy) methyl) -4-methoxyphenyl). 26 g (55% yield) of diphenyl sulfone was obtained.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.89 (s, 6H), 3.78 (t, 4H), 3.87 (s, 6H), 4.35 (t, 4H), 4. 65 (s, 4H), 5.49 (br, 2H), 6.09 (br, 2H), 6.90-6.98 (m, 2H), 7.45-7.51 (m, 2H) 7.60-7.72 (m, 8H), 7.94-8.02 (m, 4H)

[Example 9]
A specific method for synthesizing the compound synthesized in Example 9 will be described below.

  (1) In Example 8 (1), 2- (4-chlorobutoxy) tetrahydro-2H-pyran (9.0 ml) shown below was used instead of 2- (2-bromoethoxy) tetrahydro-2H-pyran. used. Except this, synthesis was performed in the same manner as in Example 8 (1) to obtain a pale yellow liquid product. In this example, the amounts of sodium hydride (55%) and intermediate compound D4 used are 2.8 g and 8.0 g, respectively. The pale yellow liquid thus obtained was used as such in the next step.

  (2) In Example 8 (2), except that the light yellow liquid obtained in Example (1) was used instead of the light yellow liquid obtained in Example 8 (1). Produced white crystals in the same manner as in Example 8 (2). The white solid thus obtained was used as such in the next step.

  (3) In Example 8 (3), the white solid obtained in Example (2) was used instead of the white solid obtained in Example 8 (2). Except for this, the compound shown below, ie, 4,4′-bis ((3- (4-methacryloyloxybutoxy) methyl) -4-methoxyphenyl, was obtained in the same manner as in Example 8 (2). ) 6.7 g (53% yield) of diphenylsulfone was obtained.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.89 (s, 6H), 2.24 (dt, 4H), 3.73 (t, 4H), 3.85 (s, 6H), 4. 32 (t, 4H), 4.65 (s, 4H), 5.49 (br, 2H), 6.09 (br, 2H), 6.91-6.99 (m, 2H), 7.45 -7.52 (m, 2H), 7.59-7.72 (m, 8H), 7.93-8.02 (m, 4H)

[Comparative Example 1]
The following compounds were synthesized and experiments for optical properties and practicality described later were conducted. Below, the synthesis | combining method of the compound of this comparative example is demonstrated.

(1) The following reagents and solvents were charged into the reaction vessel.
Intermediate compound D3: 5 g
4-hydroxyphenylboronic acid: 2.5 g
Sodium bicarbonate: 4g
Dioxane: 200ml
Water: 100ml
Tetrakistriphenylphosphine palladium: 0.3g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature (90 ° C.) for 20 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, an aqueous ammonium chloride solution was added to stop the reaction, and then the organic layer was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography to obtain 4.2 g of 4- (4-hydroxyphenyl) -4′-hydroxydiphenylsulfone (yield 98%). )Obtained.

(2) The following reagents and solvents were charged into the reaction vessel.
Sodium hydride: 1.2g
N, N-dimethylformamide: 150 ml

  Next, after cooling the reaction solution to 0 ° C., 4.2 g of 4- (4-hydroxyphenyl) -4′-hydroxydiphenyl sulfone synthesized in (1) was slowly added at the same temperature (0 ° C.). Next, the reaction solution was stirred for 2 hours while warming to room temperature. Next, after adding 4.8 ml of 2- (2-bromoethoxy) tetrahydro-2H-pyran, the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 12 hours. At this time, the progress of the reaction was confirmed by TLC. Next, an aqueous ammonium chloride solution was added to stop the reaction, and then the organic layer was extracted with ethyl acetate. Next, the obtained organic layer was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure was purified by column chromatography. The product thus obtained was used as such in the next step.

(3) The product obtained in (2) and the reagents and solvents shown below were charged into the reaction vessel.
Tetrahydrofuran: 10ml
Methanol: 40ml
P-Toluenesulfonic acid: small amount

  Next, the reaction solution was stirred at room temperature for 12 hours. At this time, the progress of the reaction was confirmed by TLC as needed. Next, the produced precipitate is filtered and collected, and then recrystallized and purified with a mixed solvent of chloroform / hexane to give 4- (4- (2-hydroxyethyloxy) phenyl) -4 ′-(2-hydroxyethyl). 5.0 g (yield 92%) of oxy) diphenylsulfone was obtained.

(4) The following reagents and solvents were charged into the reaction vessel.
4- (4- (2-hydroxyethyloxy) phenyl) -4 ′-(2-hydroxyethyloxy) diphenylsulfone: 4.0 g
Methacrylic acid: 25 ml
Paratoluenesulfonic acid: 0.2 g
4-methoxyphenol: 0.2 g
Toluene: 30ml

  Next, the reaction solution was heated and stirred for 20 hours. In addition, the water | moisture content produced | generated at this time was removed suitably, and reaction progress was confirmed at any time by TLC. Next, an aqueous sodium hydroxide solution was added to neutralize the reaction solution, and then the organic phase was extracted with chloroform. Next, the obtained organic phase was washed with water and saturated brine in that order, and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by concentrating the organic layer under reduced pressure is purified by column chromatography to give 4- (4- (2-methacryloyloxyethyloxy) phenyl) -4 ′-(2-methacryloyloxy). 4.3 g (81% yield) of ethyloxy) diphenylsulfone was obtained.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 1.92 (s, 3H), 1.95 (s, 3H), 4.20-4.29 (m, 4H), 4.46-4.52 (M, 4H), 5.58 (d, 1H), 5.58 (d, 1H), 6.12 (d, 1H), 6.12 (d, 1H), 6.94-7.03 ( m, 4H), 7.47-7.54 (m, 2H), 7.61-7.67 (m, 2H), 7.88-7.97 (m, 4H)

[Comparative Example 2] Synthesis of 4,4'-bis (2-methylthiophenyl) diphenylsulfone A compound shown below (4,4'-bis (2-methylthiophenyl) diphenylsulfone) was synthesized and optical properties described later. And practicality experiments were conducted. Below, the synthesis | combining method of the compound of this comparative example is demonstrated.

(1) The following reagents and solvents were charged into the reaction vessel.
4,4'-dichlorodiphenyl sulfone: 0.4 g
2-methylthiophenylboronic acid: 0.6 g
Sodium bicarbonate: 0.8g
1,4-dioxane: 20 ml
Water: 10ml
Tetrakistriphenylphosphine palladium: 0.07g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature for 20 hours. still. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after diluting the reaction solution with water, the organic layer was recovered by solvent extraction. Next, the obtained organic layer was washed with water and saturated brine in this order. Next, the obtained organic phase was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. Next, the crude product was recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain 0.5 g of 4,4′-bis (2-methylthiophenyl) diphenylsulfone as pale yellow crystals (yield 72). %)Obtained.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 2.37 (s, 6H), 7.14-7.40 (m, 8H), 7.56-7.62 (m, 4H), 8.00 -8.06 (m, 4H)

[Comparative Example 3] Synthesis of 4- (4-methylthiophenyl) diphenyl ether The following compound (4- (4-methylthiophenyl) diphenyl ether) was synthesized, and experiments for optical properties and practicality described later were performed. Below, the synthesis | combining method of the compound of this comparative example is demonstrated.

(1) The following reagents and solvents were charged into the reaction vessel.
4-bromodiphenyl ether: 0.8 g
4-methylthiophenylboronic acid: 0.6 g
Sodium bicarbonate: 0.8g
Dioxane: 20ml
Water: 10ml
Tetrakistriphenylphosphine palladium: 0.1 g

  The reaction solution was then heated to 90 ° C. and stirred at this temperature for 20 hours. still. At this time, the progress of the reaction was confirmed by TLC as needed. Next, after diluting the reaction solution with water, the organic layer was recovered by solvent extraction. Next, the obtained organic layer was washed with water and saturated brine in this order. Next, the obtained organic phase was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. Next, this crude product was recrystallized and purified with a mixed solvent of hexane / ethyl acetate to obtain 0.8 g (yield 89%) of 4- (4-methylthiophenyl) diphenyl ether.

About the obtained compound, the structure was confirmed by < ¹ > H-NMR.

¹ H-NMR (CDCl ₃ ; TMS): δ 2.51 (s, 3H), 7.03-7.15 (m, 4H), 7.28-7.39 (m, 5H), 7.46 -7.55 (m, 4H)

[Evaluation of optical properties]
The optical properties of the compounds synthesized in Examples and Comparative Examples were evaluated by the following methods.

(1) Production of Evaluation Sample First, an evaluation sample was produced by the following method.

(1a) Sample for refractive index measurement Two disc-shaped glass substrates having a diameter of 20 mm are prepared, and the first glass substrate is prepared so that the compound to be measured has a uniform thickness of 12.5 μm. Placed on top. Next, after placing the second glass substrate on the compound to be measured, the outer peripheral portion of the glass substrate was sealed. Here, when the compound to be measured was a (meth) acrylate compound, the compound sandwiched between the two glass substrates was cured by irradiating the sample with ultraviolet light. On the other hand, when the compound to be measured is a compound other than the (meth) acrylate compound, the sample was heated to melt the compound sandwiched between the two glass substrates.

(1b) Transmittance measurement sample In (1a) above, the substrate to be prepared is a disc-shaped glass substrate having a diameter of 50 μm, and the thickness of the compound to be measured placed on the first glass substrate is 500 μm. A sample was prepared by the same method as in (1a) except for the above.

(2) Measurement and evaluation The refractive index was measured using an Abbe refractometer (Kalnew Optical Industry). Further, the transmittance was obtained by forming two types of films having different optical path lengths, measuring them with a spectrophotometer U-4000 (product name) manufactured by Hitachi High-Technology Co., Ltd., and converting them to an internal transmittance (410 μm) at 410 nm. Is shown in the table. Here, the optical characteristics within the range B in FIG. 1 and the transmittance at 410 nm of 90% or more were evaluated as comprehensive evaluation ◯, and the others were evaluated as comprehensive evaluation ×. The results are shown in Table 1.

[Evaluation of stability]
Stability was evaluated as “◯” when there was no alteration when stored at 25 ° C. in the atmosphere for 2 weeks, and “x” when altered. However, those having a polymerizable substituent are determined in a state where a small amount (1000 ppm or less) of a polymerization inhibitor is contained. The results are shown in Table 1.

The organic compound for optical materials and the optical material of the present invention have high refractive index dispersion characteristics (Abbe number (ν _d )) and secondary dispersion characteristics (θg, F) (high θg, F characteristics), and have a chromatic aberration correction function. It has high characteristics. For this reason, it can utilize for the apparatus which has several lenses, such as a camera lens.

  10: Optical member, 20 (30, 40): Lens substrate

Claims (19)

Following general formula (1) for optical material organic compound which is a compound represented by (excluding 2,2-bis (4-acryloyloxy ethoxy-biphenyl) sulfone.).

(In Formula (1), X and Y are substituents each selected from the substituent shown below.

(* Represents a bond with R ₁ or R ₂ )
R ₁ and R ₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group. Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an unsubstituted alkyl group having 1 to 2 carbon atoms, and the following formula (3): It is a substituent selected from the substituents shown.

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
a and b are integers of 0 to 2, respectively. When a is 2, the two Z ₁ may be the same or different. When b is 2, the two Z ₂ may be the same or different. ) X and Y are the substituents respectively selected from the substituent shown below, The organic compound for optical materials of Claim 1 characterized by the above-mentioned.

(* Represents a bond with R ₁ or R ₂ ) X and Y are the substituents respectively selected from the substituent shown below, The organic compound for optical materials of Claim 1 or 2 characterized by the above-mentioned.

(* Represents a bond with R ₁ or R ₂ ) R ₁ and R ₂ are each a hydrogen atom or a (meth) acryloyl group,
X and Y are each a substituent selected from the substituents shown below,
Z ₁ and Z ₂ are each a substituent selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and an alkyl group having 1 to 2 carbon atoms. the optical material for an organic compound according to any one of claims 1 to 3, characterized.

(* Represents a bond with R ₁ or R ₂ ) X and Y are each -S- or -O-;
R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
Z ₁ and Z ₂ are each a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an unsubstituted alkyl group having 1 to 2 carbon atoms, and the following formula (3): A substituent selected from the substituents shown

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
The organic compound for optical materials according to claim 1, wherein X and Y are each -S- or -O-;
R ₁ and R ₂ are each a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
Z ₁ and Z ₂ are each a hydrogen atom or an unsubstituted alkyl group having 1 to 2 carbon atoms and a substituent selected from the substituent represented by the following formula (3)

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
The organic compound for optical materials according to claim 1 or 5, wherein X and Y are each -S- or -O-;
R ₁ and R ₂ are each an alkyl group having 1 to 2 carbon atoms,
Z ₁ and Z ₂ are each a hydrogen atom or an unsubstituted alkyl group having 1 to 2 carbon atoms and a substituent selected from the substituent represented by the following formula (3)

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
The organic compound for an optical material according to claim 1, wherein the organic compound is an optical material. Z ₁ and / or Z ₂ is an organic optical material according to any one of claims 1 to 3 and claims 5 to 7, characterized in that a substituent represented by the following general formula (3) Compound.

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.) An organic compound for optical materials represented by the following general formula (2):

(In Formula (2), X is a substituent selected from the substituents shown below.

(* Represents a bond with R ₁₁ )
Y is a substituent selected from the substituents shown below.

(* Represents a bond with R ₁₂ )
R ₁₁ and R ₁₂ are each a substituent selected from a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and a (meth) acryloyl group. Z ₃ is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an unsubstituted alkyl group having 1 to 2 carbon atoms, or a substituent represented by the following formula (3). Is the selected substituent.

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.)
c is an integer of 0 to 2. When c is 2, the two Z ₃ may be the same or different. ) X is a substituent selected from the substituents shown below,

(* Represents a bond with R ₁₁ )
The organic compound for an optical material according to claim 9, wherein Y is a substituent selected from the following substituents.

(* Represents a bond with R ₁₂ ) X is a substituent shown below,

(* Represents a bond with R ₁₁ )
The organic compound for optical materials according to claim 9 or 10, wherein Y is a substituent shown below.

(* Represents a bond with R ₁₂ ) X is a substituent shown below,

(* Represents a bond with R ₁₁ )
Y is a substituent shown below,

(* Represents a bond with R ₁₂ )
R ₁₁ and R ₁₂ are a hydrogen atom or a (meth) acryloyl group,
Z ₃ is a substituent selected from a hydrogen atom, a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, and an alkyl group having 1 to 2 carbon atoms, The organic compound for optical materials as described in any one of Claims 9 thru | or 11. Z ₃ is an optical material for an organic compound according to any one of claims 9 to 11, characterized in that a substituent represented by the following general formula (3).

(In Formula (3), ** represents a bond, m is 0 or 1, n is an integer of 2 to 4, and R is hydrogen or a methyl group.) The organic compound for optical materials according to claim 8 or 13, wherein m is 0. Optical material characterized by containing an optical material for an organic compound according to any one of claims 1 to 14. An optical material comprising: a polymer; and the organic compound for an optical material according to any one of claims 1 to 14 contained in the polymer. An optical material having a compound obtained by polymerizing the organic compound for optical material according to any one of claims 1 to 14,
An optical material, wherein the organic compound for an optical material has an acryloyl group. An optical material having a compound obtained by copolymerizing the organic compound for optical material according to any one of claims 1 to 14,
An optical material, wherein the organic compound for an optical material has an acryloyl group. An optical element obtained by molding the optical material according to any one of claims 15 to 18 .

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