JP2003081958A - Diphenyl sulfide derivative having oxetane ring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical material having a high refractive index by which optical instruments such as microscopes, cameras and telescopes and display material such as Fresnel lens, lenticular lens, prism sheets, optical waveguides and diffusion sheets and lens systems can be small-sized and lightened, and chromatic aberration due to spherical lens can be minimized. SOLUTION: This diphenyl sulfide having oxetane ring is represented by formula (1) [wherein R1 to R8 are each hydrogen atom, a halogen atom or a 1-6C alkyl group; R9 and R10 are each hydrogen atom or a 1-6C alkyl group and they may mutually be same or different; Z is oxygen atom or sulfur atom] and has a high refractive index. A method for producing the compound is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound having an oxetane ring capable of cationic polymerization and a method for producing the same, and a photocurable resin and a thermosetting resin having a high refractive index can be obtained. The present invention relates to a curable composition containing the compound.

[0002]

2. Description of the Related Art In recent years, synthetic resins have been widely used as various optical materials because they are lighter in weight and easier to handle than inorganic glasses. In various physical properties required as optical materials,
High transparency, high refractive index, strong strength, impact resistance, low specific gravity and good workability are extremely important. The optical material having a high refractive index makes it possible to make the optical system such as a microscope, a photographer and a telescope, and the lens system occupying an important position in the spectacle lens compact, and to reduce the weight. Further, with this material, the display material such as the Fresnel lens, the lenticular lens, the prism sheet, the light guide plate and the diffusion sheet can be made compact, and the weight can be reduced. In addition, it becomes possible to suppress the chromatic aberration due to the spherical lens or the like.

A compound having an oxetane ring (hereinafter referred to as an oxetane compound) is a compound that has recently attracted attention as a monomer capable of undergoing cationic polymerization and curing, and many oxetane compounds having one or a plurality of oxetane groups. It has been reported. For example, Pure Appl. Che
m., A29 (10), pp.915 (1992) and Pure Appl. Chem., A3
0 (2 & 3), pp. 189 (1993) describes a method for synthesizing various oxetane compounds. Further, DE 1,021,858 discloses an oxetane compound represented by the following formula (4).

[0004]

[Chemical 4]

In the formula (4), R ₁₂ is an aromatic residue having a valence of 1 or 2, and n is 1 or 2.

Further, JP-A-6-16804 discloses an oxetane compound represented by the following formula (5).

[0007]

[Chemical 5]

In the formula (5), R ₁₃ is a hydrogen atom and has 1 to 10 carbon atoms.
6 represents an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, a furyl group, a thienyl group or a fluorine atom, and R ₁₄ is a chain or branched poly (alkyleneoxy)
Represents a polyvalent group selected from the group consisting of a group, a xylylene group, a siloxane bond and an ester bond, Z represents an oxygen atom or a sulfur atom, and m is 2, 3 or 4.

However, the above-mentioned oxetane compounds and the like have a low refractive index, and there is room for improvement when used as an optical material.

[0010]

[PROBLEMS TO BE SOLVED] To provide a diphenyl sulfide derivative having an oxetane ring represented by the following formula (1) having a high refractive index and a method for producing the same.

[0011]

[Chemical 6]

In the formula (1), R _{1 to} R ₈ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₉ and R ₁₀ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. And these may be the same or different from each other, and Z represents an oxygen atom or a sulfur atom.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The diphenyl sulfide derivative having an oxetane ring in the present invention is a compound represented by the above formula (1), wherein R _{1 to} R ₈ in the formula (1) are hydrogen atom, fluorine atom or chlorine. A halogen atom such as an atom, or an alkyl group having 1 to 6 carbon atoms, which may or may not have a branch, and among these, a hydrogen atom or a methyl group is preferred from the viewpoint of easy availability of raw materials. preferable. R ₉ and R ₁₀ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may or may not be branched, and among these, a methyl group and an ethyl group are preferred from the viewpoint of easy availability of raw materials. Is preferred.

The method for producing the diphenyl sulfide derivative having an oxetane ring of the present invention is represented by the following formula (2) in the presence of alkali, that is, in the presence of alkali metal hydroxide, alkali metal hydride or alkali metal. Examples thereof include a method of reacting a compound with a compound represented by the following formula (3), or reacting the compound represented by the formula (2) with an alkali, that is, an alkali metal hydroxide, an alkali metal hydride or an alkali metal. And the like to form an alkali metal salt, and the alkali metal salt is converted to the formula (3)
A method of reacting with a compound represented by

[0015] When synthesizing the compounds of the formula (1), compounds represented by formula (3) using a mixture of R ₁₁ is different, even in addition to the sequentially combined reaction system a compound R ₁₁ is different good.

If necessary in these reactions, an organic solvent may be used, and it is particularly preferable to use an aromatic hydrocarbon solvent, for example, benzene, toluene and xylene are preferably used.

[0017]

[Chemical 7]

In the formula (2), R _{1 to} R ₈ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may or may not be branched, and these may be the same or different from each other. It may be. Z represents an oxygen atom or a sulfur atom.

The compound represented by the formula (2) includes bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide and 4,4 '.
-Thiodi (2,6-dimethylphenol), 4,4'-
Thiodi (2-tert-butyl-6-methylphenol), 4,4′-thiodi (2,6-ditertiarybutylphenol), 4,4′-thiodibenzenethiol and the like can be mentioned, which were also obtained. From the viewpoint of the refractive index and cationic polymerizability of the compound, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-)
Methylphenyl) sulfide and 4,4′-thiodibenzenethiol are preferred.

[0020]

[Chemical 8]

In the formula (3), R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may or may not be branched.

The compound represented by the formula (3) is 3-chloromethyl-3-methyloxetane in which R ₁₁ is a methyl group and 3-chloromethyl- in which R ₁₁ is an ethyl group because of easy availability.
3-ethyloxetane and the like are preferable, and these are disclosed in JP-A-1
It can be produced by a known method such as 0-204071 or JP-A-10-212282.

The alkali used when synthesizing the compound represented by the formula (1) from the formulas (2) and (3) includes sodium hydroxide and potassium hydroxide as the alkali metal hydroxide. These alkali metal hydroxides can be used in a powdered state or in an aqueous solution of 5 to 60% by weight, particularly preferably in an aqueous solution of 40 to 50% by weight, and examples of the alkali metal hydride include sodium hydride and potassium hydride. Examples of the alkali metal include metallic sodium and metallic potassium.
The amount of the alkali metal hydroxide or the like used is preferably 1 to 4 mol with respect to 1 mol of the compound of the formula (2),
More preferably, it is 1.0 to 2.0 mol.

When an aqueous alkaline solution is used in the above synthesis reaction, a phase transfer catalyst may be used for the purpose of increasing the reaction rate. As the phase transfer catalyst, a known phase transfer catalyst (for example, WP Weber, GW Gokel) is used.
Co-authored by Iwao Tafushi and Takako Nishitani, "Phase Transfer Catalyst", Inc.
Although those described in Kagaku Dojin, etc.) can be used, among them, organic quaternary ammonium salts and phosphonium salts are preferable because of their high ability as catalysts. Specific examples include tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, benzyltriethylammonium chloride, trioctylmethylammonium chloride, tetra-n-.
Butylphosphonium bromide, trioctylethylphosphonium chloride, tetraphenylphosphonium chloride and the like can be mentioned. The amount of the phase transfer catalyst used is preferably 0.1 to 30% by weight, and particularly preferably 1 to 10% by weight relative to the compound of formula (2).

The reaction temperature in the above reaction is 50 to 150.
C. is preferable, and particularly preferably 70 to 120.
℃. The reaction time is preferably 1 to 10 hours, depending on the reaction temperature.

When synthesizing the compound represented by the formula (1), it is preferable to remove oxidizing substances such as oxygen from the reaction system in order to suppress side reactions, and particularly, as the compound of the formula (2), When a thiol compound such as 4′-thiodibenzenethiol is used, it is particularly preferable to remove an oxidizing substance such as oxygen from the reaction system in order to suppress side reactions.

After completion of the synthesis reaction, the organic layer or the organic solid is taken out by cooling to room temperature, washed with water and dried to obtain the desired diphenyl sulfide derivative having an oxetane ring. The structure of the obtained compound can be confirmed by high resolution nuclear magnetic resonance.

The compound of the present invention can be used as a curable composition containing the compound or can be compounded with another curable compound and polymerized. When compounded, the ratio of the compound of the present invention is 20 to 9 relative to 100 parts by weight of the curable composition.
5 parts by weight is preferred. The compound of the present invention can also be cationically polymerized, and this cationic polymerization can be carried out by heating or irradiation with energy rays (visible light, ultraviolet rays, electron rays or the like). At this time, it is desirable to add a cationic polymerization initiator. The cationic polymerization initiator includes a thermal cationic polymerization initiator or an active energy ray cationic polymerization initiator. The active energy ray cationic polymerization initiator can be used without particular limitation as long as it is a compound that produces an acid by the action of active energy rays. For example, this is described in "UV / EB curable material" [published by CMC (1992)]. Of these, diaryl iodonium salts and triaryl sulfonium salts are preferable, but they can be used without limitation. The curable compound to be blended is not limited to the cationic curable compound.

The curable composition containing the compound of the present invention further comprises a release agent, a defoaming agent, a leveling agent, a light stabilizer (eg hindered amine), an antioxidant, a polymerization inhibitor,
An antistatic agent, an adhesion improver (for example, various polymers) and the like can be added.

Photocurable resins and thermosetting resins which can be obtained from the curable composition containing the compound of the present invention having a high refractive index are considered to have a high refractive index, and are used for eyeglass plastic lenses, Fresnel lenses and lenticular lenses. It is useful as an optical material such as a lens, an optical disk substrate, a plastic optical fiber, an LCD prism sheet, a light guide plate, and a diffusion sheet. The curable composition containing the compound is also useful as a raw material for paints, adhesives, encapsulants and the like.

[0031]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 10 equipped with a thermometer, a condenser, a stirrer and a dropping funnel
In a 00 mL three-necked round bottom flask, 123.2 g of bis (4-hydroxy-3-methylphenyl) sulfide.
(0.5 mol), 3-chloromethyl-3-ethyloxetane (269.2 g, 2.0 mol) and tetrabutylammonium bromide (6.4 g) as a catalyst were added, and the mixture was stirred at room temperature. To this, 140.3 g (1.2 mol) of 48 wt% potassium hydroxide aqueous solution was added dropwise from the dropping funnel over 2 hours. After the dropping, raise the temperature until reflux.
(Outer bath temperature: about 120 ° C.) The reaction was continued for 4 hours. After 4 hours, cool the reaction mixture to room temperature and add 400 mL of pure water.
After adding and stirring well, the mixture was separated into an oil layer and an aqueous layer with a separating funnel. The oil layer was washed 5 times with 500 mL of water. Then, the low-boiling component is removed under reduced pressure at 120 ° C.
5.4 g of a pale yellow liquid was obtained. GPC analysis (column: G
PC-803 or GPC-802 (manufactured by Shimadzu Corporation),
Elution solvent: tetrahydrofuran, flow rate: 1 mL / mi
(n, detection: differential refraction), the compound obtained had a purity of 98% and a yield of 61 mol%. From the results of high resolution nuclear magnetic resonance ( ¹ H-NMR, 270 MHz),
It was determined to be a compound represented by the following formula (6).

[0033]

[Chemical 9]

High resolution nuclear magnetic resonance ( ¹ H-NMR, 27
The results of measurement at 0 MHz) are shown below (tetramethylsilane was used as a reference substance and deuterated chloroform was used as a solvent for this measurement).

[0035] No. ppm Cleaved state Proton number Attribution 1 7.257 1 doublet 2 (h) 2 7.176-7.154 doublet 2 (g) 2 6.799-6.765 Double line 2 (f) 3 4.592-4.471 Multiple line 8 (e) 4 4.058 Single line 4 (d) 5 2.173 Single line 6 (c) 6 1.936-1.852 Multiple line 4 (b) 7 0.968-0.912 Triple line 6 (a)

Example 2 10 equipped with a thermometer, a cooler, a stirrer and a dropping funnel
In a 00 mL three-necked round bottom flask, 125.2 g (0.5 mol) of 4,4-thiodibenzenethiol and 269.2 g (2.0 mol) of 3-chloromethyl-3-ethyloxetane.
mol) and blow dry nitrogen at 80 ° C for 2
The mixture was heated and stirred for an hour. 48% by weight after cooling to room temperature
140.3 g (1.2 mol) of potassium hydroxide aqueous solution
Was dropped from the dropping funnel over 2 hours. After the completion of the dropping, the temperature was raised until reflux (outer bath temperature: about 120 ° C.), and the reaction was continued for 2 hours. After 2 hours, the reaction mixture was cooled to room temperature,
After adding 400 mL of pure water and stirring well, the mixture was separated into an oil layer and an aqueous layer with a separating funnel. This oil layer is mixed with 500 mL of water 5
Washed twice. Then, the low boiling point component was removed at 120 ° C. under reduced pressure to obtain 150.6 g of a pale yellow liquid. As a result of GPC analysis (analytical conditions were the same as in Example 1), the purity of the obtained compound was 98.9%, and the yield was 67 mol%. High resolution nuclear magnetic resonance ( ¹ H-NMR, 270 MH
From the result of z), it was determined to be a compound represented by the following formula (7).

[0037]

[Chemical 10]

High resolution nuclear magnetic resonance ( ¹ H-NMR, 27
The results of measurement at 0 MHz) are shown below (tetramethylsilane was used as a reference substance and deuterated chloroform was used as a solvent for this measurement).

[0039] No. ppm Cleaved state Proton number Attribution 1 7.323-7.218 Multiple line 8 (e) 2 4.441-4.378 multiple lines 8 (d) 3 3.284 Single line 4 (c) 4 1.881-1.799 Multiple line 4 (b) 5 0.918-0.863 Triple line 6 (a)

The refractive index of the oxetane compounds obtained in Examples 1 and 2 was measured at 25 ° C. using an Abbe refractometer.

As a result, the oxetane compound obtained in Example 1 had a refractive index of 1.57, and the compound obtained in Example 2 had a refractive index of 1.63.

When the refractive index of the comparative oxetane compound was measured, it was found to be 1,4-bis [[(3-ethyl-3-oxetanyl) methoxy] methyl] benzene ("Aron Oxetane OXT-121" manufactured by Toagosei Co., Ltd.). ) Was 1.51, and the refractive index of 3-ethyl-3-phenoxymethyl oxetane (“Aron oxetane OXT-211” manufactured by Toagosei Co., Ltd.) was 1.52.

As is clear from the above results, Example 1
And all the compounds obtained in Example 2 have a high refractive index as compared with the oxetane compound compared.

[0044]

INDUSTRIAL APPLICABILITY The diphenyl sulfide derivative having an oxetane ring of the present invention can be cured by light or heat, and a photocurable resin and a thermosetting resin obtained from or containing these compounds are High refractive index, plastic lens for glasses, Fresnel lens,
It is useful as an optical material such as a lenticular lens, an optical disk substrate, a plastic optical fiber, an LCD prism sheet, a light guide plate and a diffusion sheet, and a raw material for paints, adhesives, encapsulating materials and the like.

Claims (2)

[Claims] 1. A diphenyl sulfide derivative having an oxetane ring, which is represented by the following formula (1). [Chemical 1] (In the formula (1), R _{1 to} R ₈ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₉ and R ₁₀ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, These may be the same or different from each other, and Z represents an oxygen atom or a sulfur atom). 2. The diphenyl sulfide having an oxetane ring according to claim 1, wherein the compound represented by the following formula (2) is reacted with the compound represented by the following formula (3) in the presence of an alkali. Method for producing derivative. [Chemical 2] (In the formula (2), R _{1 to} R ₈ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different, and Z is an oxygen atom or sulfur. Indicates an atom). [Chemical 3] (In the formula (3), R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)