JP2011046820A - Sulfur-containing compound and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monomer having a high refractive index and capable of forming a resin for an optical member such as a lens. <P>SOLUTION: A sulfur-containing compound has a structure represented by -NH-C(=S)-S-. The preferable example thereof is a compound represented by formula (1) wherein A is a 1-8C divalent organic group; B is a 2-12C n-valent organic group which may contain a hetero atom such as a sulfur atom; Z is an oxygen atom or a sulfur atom; R<SP>1</SP>is a hydrogen atom or a methyl group; and n is an integer of 1 to 4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sulfur-containing compound such as a sulfur-containing (meth) acrylate compound for use as a raw material for optical components such as lenses, and a method for producing the same.

Plastic lenses are widely used in applications such as eyeglass lenses and camera lenses because they have features such as being light and hard to break compared to lenses made of inorganic materials such as glass.
In recent years, an optical resin having a higher refractive index has been demanded as a plastic lens material under the circumstances that the center thickness of a spectacle lens tends to be reduced.
In order to obtain an optical resin (polymer) having such a high refractive index, it is known to use a compound containing a sulfur atom as a monomer (Patent Documents 1 and 2).

JP 2007-211021 A JP-A-8-325337

Conventionally, in order to obtain a radiation curable compound having a high refractive index, a complicated process has been required.
The present invention provides a sulfur-containing compound which is a monomer having a high refractive index and capable of forming an optical member such as a lens and which can be produced with a small number of steps. With the goal.

（式中、Ａは炭素数１〜８の２価の有機基、Ｂはヘテロ原子を含んでいても良い炭素数２〜１２のｎ価の有機基、Ｚは酸素原子または硫黄原子、Ｒ^１は水素原子またはメチル基、ｎは１〜４の整数である。）
［３］ 前記Ｂが下記の一般式（２）で表される前記［２］に記載の化合物。
−Ｒ^２−（Ｓ−Ｒ^２）_ｍ− （２）
（式中、Ｒ^２は炭素数２〜４のアルキレン基を示し、ｍは０〜２の整数である。）
［４］ 屈折率ｎ_Ｄが１．６０以上である前記［１］〜［３］のいずれかに記載の化合物。
［５］ チオシアナート基、及び（メタ）アクリロイル基を導入可能な官能基を有する化合物と、チオール含有化合物を反応させて、−ＮＨ−Ｃ（＝Ｓ）−Ｓ−結合及び前記官能基を有する化合物を得た後、前記官能基に対して（メタ）アクリロイル基を導入する、前記［１］〜［４］のいずれかに記載の化合物の製造方法。
［６］ 前記［１］〜［４］のいずれかに記載の化合物を含む組成物を重合させてなる硬化体。
［７］ 前記［６］に記載の硬化体からなる光学部材。 The present inventor has found that the above problems can be solved by a sulfur-containing compound having a specific chemical structure, and has completed the present invention.
That is, the present invention provides the following [1] to [6].
[1] A sulfur-containing compound having a structure represented by —NH—C (═S) —S—.
[2] The compound according to [1], which is represented by the following general formula (1).

(In the formula, A is a divalent organic group having 1 to 8 carbon atoms, B is an n-valent organic group having 2 to 12 carbon atoms which may contain a hetero atom, Z is an oxygen atom or a sulfur atom, R ¹ Is a hydrogen atom or a methyl group, and n is an integer of 1 to 4.)
[3] The compound according to [2], wherein B is represented by the following general formula (2).
_{^{-R 2 - (S-R 2}} ) m - (2)
(In the formula, R ² represents an alkylene group having 2 to 4 carbon atoms, and m is an integer of 0 to 2.)
[4] The compound according to any one of [1] to [3], wherein the refractive index n _D is 1.60 or more.
[5] A compound having a functional group capable of introducing a thiocyanate group and a (meth) acryloyl group, and a thiol-containing compound, thereby reacting the compound with an —NH—C (═S) —S— bond and the functional group. The method for producing a compound according to any one of [1] to [4], wherein a (meth) acryloyl group is introduced into the functional group after obtaining the above.
[6] A cured product obtained by polymerizing a composition containing the compound according to any one of [1] to [4].
[7] An optical member comprising the cured body according to [6].

According to the compound of the present invention, a liquid radiation curable composition capable of forming a cured product having a high refractive index can be prepared.
The liquid radiation curable composition can be used as a material for optical members. Specifically, it is used for materials of lenses (for example, eyeglass lenses, camera lenses, etc.), nanoimprint materials, optical adhesives, and the like. Can be used.
According to the method for producing a compound of the present invention, a target compound can be easily obtained in a short time with a small number of steps.

1 is a diagram showing a ¹ H NMR spectrum of a compound obtained in Example 1. FIG. 2 is a diagram showing an IR spectrum of the compound obtained in Example 1. FIG. 2 is a diagram showing an IR spectrum of a homopolymer of the compound obtained in Example 1. FIG.

（式中、Ａは炭素数１〜８の２価の有機基、Ｂはヘテロ原子を含んでいても良い炭素数２〜１２のｎ価の有機基、Ｚは酸素原子または硫黄原子、Ｒ^１は水素原子またはメチル基、ｎは１〜４の整数である。）
前記の一般式中、Ａは、炭素数１〜８、好ましくは、屈折率の観点から炭素数１〜４の２価の有機基である。Ａの好ましい例としては、メチレン基または炭素数２〜４のアルキレン基が挙げられる。
Ｂは、ヘテロ原子を含んでいても良い炭素数２〜１２、好ましくは、高い屈折率を得やすいことから、炭素数２〜４の有機基である。ヘテロ原子としては、硫黄原子、酸素原子、窒素等が挙げられる。Ｂの好ましい例としては、硫黄原子を含んでいても良い炭素数２〜８の有機基が挙げられる。
ｎは１〜４、好ましくは、反応の効率性の観点から２〜４の整数である。
ｎが２の場合、Ｂの例として、下記式（２）の構造が挙げられ、このうち、−ＣＨ₂−ＣＨ₂−Ｓ−ＣＨ₂−ＣＨ₂−が好ましい。
−Ｒ^２−（Ｓ−Ｒ^２ ）_ｍ− （２）
式（２）中、Ｒ^２は炭素数２〜４のアルキレン基を示し、ｍは０〜２の整数である。 The compound of the present invention has a structure represented by -NH-C (= S) -S-.
Preferred examples of the compound of the present invention include those represented by the following general formula (1).

(In the formula, A is a divalent organic group having 1 to 8 carbon atoms, B is an n-valent organic group having 2 to 12 carbon atoms which may contain a hetero atom, Z is an oxygen atom or a sulfur atom, R ¹ Is a hydrogen atom or a methyl group, and n is an integer of 1 to 4.)
In said general formula, A is C1-C8, Preferably, it is a C1-C4 bivalent organic group from a viewpoint of a refractive index. Preferable examples of A include a methylene group or an alkylene group having 2 to 4 carbon atoms.
B is an organic group having 2 to 12 carbon atoms, which may contain a hetero atom, and preferably 2 to 4 carbon atoms because a high refractive index is easily obtained. Examples of the hetero atom include a sulfur atom, an oxygen atom, and nitrogen. Preferable examples of B include organic groups having 2 to 8 carbon atoms which may contain a sulfur atom.
n is an integer of 1 to 4, preferably 2 to 4 from the viewpoint of reaction efficiency.
When n is 2, examples of B include the structure of the following formula (2), and among them, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ — is preferable.
-R ² - ^{(S-R 2} ) _M- (2)
In formula (2), R ² represents an alkylene group having 2 to 4 carbon atoms, and m is an integer of 0 to 2.

As an example of the method for producing the compound of the present invention, a compound having a thiocyanate group (chemical formula: —NCS) and a functional group capable of introducing a (meth) acryloyl group is reacted with a thiol-containing compound to produce —NH—C After obtaining a compound having a (= S) -S-bond and the functional group, a (meth) acryloyl group is introduced into the functional group to obtain a target (meth) acrylate compound. .
An example of this method is shown in the following synthesis flow. In the following synthesis flow, the compound denoted by reference numeral 1 is hereinafter referred to as “compound 1”. Similarly, the compounds denoted by reference numerals 2 to 5 are referred to as “compound 2” to “compound 5”.

In the above synthesis flow, first, 2-bromoethanol is dissolved in a solvent (for example, dichloroethane), and in the presence of H ⁺ (for example, p-toluenesulfonic acid) as a catalyst, tetrahydro-2H- Reaction with pyran (also known as dihydropyran) produces compound 1.
The amount of tetrahydro-2H-pyran may be 1 or more in an equivalent ratio with respect to 2-bromoethanol. The amount of p-toluenesulfonic acid is 1 to 10 mol% with respect to 100 mol% of 2-bromoethanol. The reaction conditions are such that the concentration of 2-bromoethanol is 0.1 to 2 M, the temperature is 15 to 40 ° C., and the reaction time is 2 hours or more.

Next, Compound 1 is reacted with potassium iodide and sodium thiocyanate in a state dissolved in a solvent (for example, tetrahydrofuran; THF) to form Compound 2.
The amount of potassium iodide and sodium thiocyanate may be 1.5 or more in an equivalent ratio with respect to compound 1. The reaction conditions are such that the concentration of Compound 1 in the reaction solution during the reaction is 0.5 M or less, the temperature is 40 to 70 ° C. (when the solvent is THF), and the reaction time is 12 hours or more. As the solvent, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or the like may be used instead of THF.
In addition, the chemical formula of Compound 2, which is abbreviated in the above synthesis flow, is as follows.

Next, Compound 2 is reacted with bis (2-mercaptoethyl) sulfide in the presence of a catalyst (for example, sodium hydroxide) in a state dissolved in a solvent (for example, ethanol) to form Compound 3. Let
The amount of bis (2-mercaptoethyl) sulfide is preferably 0.4 to 0.6, more preferably 0.5, in an equivalent ratio with respect to compound 2. The reaction conditions are a temperature of room temperature (preferably 5 to 40 ° C.), a reaction time of 12 hours or more, and a nitrogen stream (essential for preventing side reactions).

Next, compound 3 is reacted with methanol in the presence of H ⁺ (eg, p-toluenesulfonic acid) as a catalyst in a state where compound 3 is dissolved in a solvent (eg, chloroform) to produce compound 4. .
The amount of methanol may be 1 or more in an equivalent ratio with respect to compound 3. The amount of p-toluenesulfonic acid is 1 to 10 mol% relative to compound 3 (100 mol%). The reaction conditions are such that the temperature is room temperature or higher (preferably 10 ° C. or higher), the reaction time is 0.5 hours or longer, and the liquidity is acidic (preferably pH 4 or lower).

Next, Compound 4 is reacted with acrylic acid chloride in the presence of a catalyst (for example, triethylamine) in a state where it is dissolved in a solvent (for example, dichloromethane) to form Compound 5.
The amounts of triethanolamine and acrylic acid chloride are each 2 or more in an equivalent ratio with respect to compound 4.
The reaction conditions are such that the temperature is 30 ° C. or less (preferably 5 to 25 ° C.) and the reaction time is 6 hours or more in order to prevent side reactions.

In the above synthesis flow, other halogenated alcohol compounds can be used in place of 2-bromoethanol used in the synthesis of Compound 1.
Examples of other halogenated alcohol compounds include 2-iodinated ethanol.
In the above synthesis flow, n (n = 1, 3 or 4) is used instead of bis (2-mercaptoethyl) sulfide, which is a compound having two mercapto groups (—SH), used in the synthesis of compound 3. ), A compound having n (n = 1, 3 or 4) (meth) acryloyl groups can be obtained.
Examples of the compound having one mercapto group include methanethiol and ethanethiol.
Examples of the compound having three mercapto groups include 2,4,6-trimercapto-S-triazine.
Examples of the compound having four mercapto groups include tetrakis (mercaptoacetoxymethyl) methane.

The refractive index n _D (liquid refractive index) of the compound of the present invention is preferably 1.60 or more.
The viscosity of the compound of the present invention is preferably 300 to 1,000 mPa · s as a value measured at 25 ° C. using a B-type viscometer.
The composition containing the compound of the present invention includes, for example, the compound of the present invention (typically, a sulfur-containing (meth) acrylate compound) and another compound (for example, a (meth) acrylate compound that does not correspond to the compound of the present invention. ) And a photopolymerization initiator.
Examples of other compounds include pentaerythritol tetraacrylate and bisphenol A-EO modified diacrylate.
Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, and the like.
The compounding ratio of each component can be, for example, 50 to 99 mass% for the compound of the present invention, 0 to 45 mass% for the other compounds, and 1 to 10 mass% for the photopolymerization initiator.

The refractive index n _D of the cured product obtained by polymerizing the composition containing the compound of the present invention is preferably 1.62 or more.

[Example 1]
According to the above synthesis flow, the desired (meth) acrylate compound (Compound 5 in the synthesis flow) was obtained using 2-bromoethanol as a starting material.
[Synthesis Method of Compound 1]
Under a nitrogen stream, 200 mL of dichloromethane was added to a 500 mL three-necked flask, and tetrahydro-2H-pyran (13.5 g, 160 mmol) and 2-bromoethanol (20 g, 160 mmol) were added. Cooled in an ice bath and p-toluenesulfonic acid (0.276 g, 1.6 mmol) was added in one portion. The mixture was then stirred at room temperature for 2 hours, and then 100 mL of water was added to the reaction mixture, and then the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, dried and filtered. Thereafter, the solvent was removed from the reaction mixture using a rotary evaporator to obtain Compound 1 (colorless transparent liquid, yield 92%, 30.8 g) in the production flow.

[Synthesis Method of Compound 2]
To a 300 mL three-necked flask equipped with a reflux tube, 160 mL of tetrahydrofuran, potassium iodide (39.9 g, 240 mmol), and sodium thiocyanate (19.5 g, 240 mmol) were added and stirred. Compound 1 (33.5 g, 160 mmol) was added in one portion and stirred overnight under reflux conditions. 100 mL of water and 150 mL of diethyl ether were added to the obtained mixture. The organic layer was separated and washed with saturated brine. After adding anhydrous magnesium sulfate to the organic layer and drying and filtering, the solvent was removed by a rotary evaporator, and the residue was distilled under reduced pressure to obtain compound 2 (light yellow transparent liquid, yield 89%) in the above production flow. )

[Synthesis Method of Compound 3]
Under a nitrogen stream, ethanol (1.1 mL) was added to a 100 mL two-necked flask, and bis (2-mercaptoethyl) sulfide (0.206 g, 1.34 mmol), 3 mL of 1M aqueous sodium hydroxide solution was added. After cooling in a water bath, Compound 2 (0.5 g, 2.67 mmol) was added and stirred at room temperature for 24 hours. 10 mL of water and 30 mL of diethyl ether were added to the reaction mixture, and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. The residue was purified by column chromatography (chloroform / hexane = 1/1 → chloroform / ethyl acetate = 8). / 1) to obtain Compound 3 (colorless transparent liquid, yield 81%) in the production flow.

[Synthesis Method of Compound 4]
Chloroform 15 mL, methanol 5 mL, and the compound 3 (1.94 g, 3.68 mmol) were added to a 100 mL eggplant flask equipped with a reflux tube, and then p-toluenesulfonic acid (38.4 mg, 0.22 mmol) was added. And stirred for 2 hours under reflux conditions. Water (15 mL) and chloroform (20 mL) were added to the reaction mixture, and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed with a rotary evaporator. The residue was recrystallized from chloroform / hexane to obtain Compound 4 (white solid, yield 71%) in the production flow.

[Synthesis Method of Compound 5]
Under a nitrogen stream, 50 mL of dichloromethane, compound 4 (3.49 g, 9.68 mmol) and triethylamine (1.96 g, 19.36 mmol) were added to a 200 mL flask equipped with a dropping funnel and stirred in a water bath. Acrylic acid chloride (2.63 g, 29 mmol) was gradually added dropwise with a dropping funnel. After stirring at room temperature overnight, saturated aqueous sodium hydrogen carbonate was added to the reaction mixture, and the mixture was stirred at room temperature for 10 minutes. After removing the solvent by distillation under reduced pressure, 100 mL of methyl isobutyl ketone was added to the residue, and 50 mL of a 10% by mass aqueous sodium hydroxide solution was added to separate the organic layer. Anhydrous magnesium sulfate was added to the organic layer, dried and filtered, and the solvent was removed with a rotary evaporator to obtain Compound 5 (white paste, yield 97%) in the production flow.

[Evaluation of Compound 5]
Measurement of Liquid Refractive Index Measurement was performed at 25 ° C. using an Abbe refractometer “NAR-4T” manufactured by Atago Co., Ltd. As a result, the refractive index of Compound 5 at a wavelength of 589 nm was 1.603.

A composition obtained by blending Compound 5 (4 g) with Irgacure 184 (trade name; manufactured by Ciba Specialty Chemicals) (0.2 g) was applied onto a glass plate using an applicator bar so that the film thickness was 200 μm. Then, a transparent cured film was obtained by irradiating ultraviolet rays of 1.0 J / cm ² under nitrogen. The refractive index of the obtained cured film was 1.625.

Claims (7)

  A sulfur-containing compound having a structure represented by —NH—C (═S) —S—. The compound of Claim 1 represented by following General formula (1).

(In the formula, A is a divalent organic group having 1 to 8 carbon atoms, B is an n-valent organic group having 2 to 12 carbon atoms which may contain a hetero atom, Z is an oxygen atom or a sulfur atom, R ¹ Is a hydrogen atom or a methyl group, and n is an integer of 1 to 4.) The compound according to claim 2, wherein B is represented by the following general formula (2).
-R ² - ^{(S-R 2} ) _M- (2)
(In the formula, R ² represents an alkylene group having 2 to 4 carbon atoms, and m is an integer of 0 to 2.) A compound according to any one of claims 1 to 3 the refractive index _{n D} is 1.60 or more.   A compound having a functional group capable of introducing a thiocyanate group and a (meth) acryloyl group was reacted with a thiol-containing compound to obtain a compound having an —NH—C (═S) —S— bond and the functional group. 5. The method for producing a compound according to any one of claims 1 to 4, wherein a (meth) acryloyl group is introduced into the functional group.   The hardening body formed by polymerizing the composition containing the compound of any one of Claims 1-4.   An optical member comprising the cured body according to claim 6.

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