JP5213100B2 - Novel sulfur-containing ethylenically unsaturated group-containing compound and polymer thereof - Google Patents

Description

  The present invention relates to a novel sulfur-containing ethylenically unsaturated group-containing compound and a polymer thereof.

  In recent years, plastic lenses that are light in weight, have high impact resistance, and can be mass-produced are increasingly used instead of inorganic glass. In the field of spectacle lenses, the proportion of plastic lenses has reached 90%. In the field of such optical lenses, a higher refractive index is being promoted for the purpose of further reducing the thickness of the lens. On the other hand, an Abbe number is one of important optical characteristics. This represents the degree of refractive index difference depending on the wavelength of light, and the higher the Abbe number, the smaller the difference and the better the lens. However, the refractive index and Abbe number of organic materials are in a trade-off relationship, and it has been difficult to improve these simultaneously.

  Further, optical lenses such as Fresnel lenses and lenticular lenses used in projection televisions have been manufactured by a method such as a press method or a cast method. However, these methods have a problem of low productivity because they require a long time for heating and cooling during production.

In order to solve such problems, in recent years, it has been studied to manufacture a lens using an ultraviolet curable resin composition. Specifically, by pouring an ultraviolet curable resin composition between a lens-shaped mold and a transparent resin substrate, by irradiating ultraviolet rays from the transparent resin substrate side and curing the composition A lens can be manufactured in a short time.
With the recent thinning and enlargement of projection televisions and video projectors, the ultraviolet curable resin composition for forming an optical lens has a high refractive index and a so-called blue loss (the screen is bluish). Phenomenon), having excellent mechanical properties, and having an appropriate viscosity (small viscosity suitable for thinning and enlargement) before curing.

  Here, as a resin composition for forming an optical lens, for example, a reaction product of a diol (a) having a specific structure, an aromatic organic polyisocyanate (b), and a hydroxyl group-containing (meth) acrylate (c). There has been proposed a resin composition comprising a urethane (meth) acrylate (A), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). (Patent Document 1).

A component: bis (acryloxymethyl or methacryloxymethyl) tricyclodecane represented by a specific general formula 40 to 80% by mass, B component: pentaerythritol tetrakis (β-thiopropionate) or pentaerythritol tetrakis ( thioglycolate) 10 to 50 mass%, C component: pentaerythritol triacrylate, trimethylolpropane triacrylate or divinyl benzene 10 to 40 mass%, obtained by polymerizing and curing a mixture of, the refractive index _(N D 20 ° C. ) Is 1.53 or more and an Abbe number (ν _D 20 ° C.) is 40 or more, a high Abbe number lens (particularly a spectacle lens) has been proposed (Patent Document 2).

  However, even with the technologies disclosed in Patent Documents 1 and 2 and the like, both the recent demand for optical lenses such as projection televisions, that is, the demand for a high refractive index due to the thinning of the optical lens and the demand for a high Abbe number are sufficiently satisfied. It is difficult to make it.

In particular, organic materials for forming optical lenses such as projection televisions generally have a higher refractive index for short-wavelength light than long-wavelength light. Therefore, if the Abbe number is small, long-wavelength light (red) is produced. In comparison, there is a problem in that short wavelength light (blue light) is refracted more greatly, and blue loss (a phenomenon in which the screen becomes bluish) occurs on a television screen. In thin rear projection televisions and the like that are becoming mainstream in recent years, the incident angle of light from the light source to the Fresnel lens becomes an acute angle, and short wavelength light is refracted more remarkably. Yes.
Note that if the Abbe number is increased in order to eliminate the problem of blue loss, the refractive index suddenly decreases, making it impossible to achieve a reduction in thickness in a projection television or the like.

JP-A-5-255464 JP-A-2-141702

  The present invention seeks to solve the above-mentioned problems of the prior art, and provides a sulfur-containing ethylenic polymer that provides a novel sulfur-containing compound and a polymer having a high refractive index and a high Abbe number. An object is to provide a saturated group-containing compound and a polymer thereof.

  In order to achieve the above object, the present inventors eagerly searched for a compound capable of simultaneously achieving a high refractive index and a high Abbe number, and a novel sulfur-containing compound having a specific structure and a compound having an ethylenically unsaturated group The present invention was completed by finding a sulfur-containing ethylenically unsaturated group-containing compound obtained by reacting with.

２．上記１に記載の含硫黄化合物と、エチレン性不飽和基を有する化合物を反応させることにより得られる含硫黄エチレン性不飽和基含有化合物。
３．前記エチレン性不飽和基が、（メタ）アクリロイル基である上記２に記載の含硫黄エチレン性不飽和基含有化合物。
４．下記式（１−１）で示される化合物からなる群から選択される上記２又は３に記載の含硫黄エチレン性不飽和基含有化合物。

（式中、Ｒは水素またはメチル基を表す。）
５．上記２〜４のいずれかに記載の含硫黄エチレン性不飽和基含有化合物を重合させることにより得られる重合体。 That is, the present invention provides the following novel sulfur-containing compounds, sulfur-containing ethylenically unsaturated group-containing compounds, and polymers thereof.
1. A sulfur-containing compound represented by the following formula (1).

2. A sulfur-containing ethylenically unsaturated group-containing compound obtained by reacting the sulfur-containing compound according to 1 and a compound having an ethylenically unsaturated group.
3. 3. The sulfur-containing ethylenically unsaturated group-containing compound according to 2 above, wherein the ethylenically unsaturated group is a (meth) acryloyl group.
4). 4. The sulfur-containing ethylenically unsaturated group-containing compound according to 2 or 3 selected from the group consisting of compounds represented by the following formula (1-1).

(In the formula, R represents hydrogen or a methyl group.)
5. The polymer obtained by polymerizing the sulfur-containing ethylenically unsaturated group containing compound in any one of said 2-4.

The novel sulfur-containing compound of the present invention can give a high refractive index and a high Abbe number to a sulfur-containing ethylenically unsaturated group-containing compound produced using this as a raw material.
The novel sulfur-containing ethylenically unsaturated group-containing compound of the present invention has a high refractive index and a high Abbe number, and is a material suitable for optical applications particularly requiring a high refractive index and a high Abbe number. .
The polymer of the present invention is obtained by polymerizing the above sulfur-containing ethylenically unsaturated group-containing compound, and provides a cured product suitable for optical applications that can simultaneously achieve a high refractive index and a high Abbe number.

  Hereinafter, the novel sulfur-containing compound, sulfur-containing ethylenically unsaturated group-containing compound, and polymer thereof of the present invention will be specifically described.

上記式（１）で示される含硫黄化合物は、高い硫黄含有率と脂環式部位を有しているため、これを用いて製造される含硫黄エチレン性不飽和基含有化合物を重合させてなる重合体を高屈折率かつ高アッベ数にすることができる。
上記式（１）で示される化合物は実施例１に記載の方法で製造することができる。 I. Sulfur-containing compound The sulfur-containing compound of the present invention is represented by the following formula (1).

Since the sulfur-containing compound represented by the above formula (1) has a high sulfur content and an alicyclic moiety, a sulfur-containing ethylenically unsaturated group-containing compound produced using this is polymerized. The polymer can have a high refractive index and a high Abbe number.
The compound represented by the above formula (1) can be produced by the method described in Example 1.

II. Sulfur-containing ethylenically unsaturated group-containing compound The sulfur-containing ethylenically unsaturated group-containing compound of the present invention comprises a sulfur-containing compound represented by the above formula (1) as one of the starting materials and a compound having an ethylenically unsaturated group. The other starting material is the compound. The polymer obtained by polymerizing the sulfur-containing ethylenically unsaturated group-containing compound of the present invention has a high refractive index and a high Abbe number.

Examples of the ethylenically unsaturated group of the other starting material containing the ethylenically unsaturated group-containing compound include a (meth) acryloyl group, a vinyl group, an N-vinyl group, an allyl group, and the like, and a (meth) acryloyl group. It is preferable that
As the ethylenically unsaturated group-containing compound, (meth) acrylic acid, (meth) acrylic acid derivatives, and the like are preferable, and (meth) acrylic acid chloride and (meth) acrylethyl isocyanate are particularly preferable.

（式中、Ｒは水素またはメチル基を表す。） As the sulfur-containing ethylenically unsaturated group-containing compound of the present invention, a compound represented by the following formula (1-1) is preferable.

(In the formula, R represents hydrogen or a methyl group.)

II. Polymer The polymer of the present invention is obtained by irradiating the sulfur-containing ethylenically unsaturated group-containing compound with radiation.
Here, the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like. A cured product is obtained by irradiating 1000 to 5000 mJ / cm ^{2 of} ultraviolet rays.

  The polymer of the present invention obtained by polymerizing the sulfur-containing ethylenically unsaturated group-containing compound of the present invention represented by the above formula (1-1) has a refractive index of 1.640 (wavelength 589.3 nm), There is no birefringence, the Abbe number is 42.1, and the material satisfies both the high refractive index and the high Abbe number at the same time.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”.

<Synthesis of sulfur-containing compounds>
Example 1
(1) Synthesis of intermediate (exo-3,5-dithiatricyclo [5.2.1.0] des-8-en-4-one)

  A solution of norbornadiene (3.66 g, 19.9 mmol), diisopropylxanthogen disulfide (13.5 g, 25 mmol) and azoisobutyronitrile (AIBN; 2 g, 25 mmol) was refluxed in toluene (500 mg) for 24 hours. The mixture was cooled to room temperature and the solvent was removed under reduced pressure. The obtained crude product was recrystallized from hexane to obtain colorless crystals (yield: 3.78 g, yield: 41%).

Melting point: 105-107 ° C
IR (KBr, ncm ⁻¹ ): 3066 (alkene C—H), 2942-2996 (alkyl C—H), 1639 (C═O)
¹ H-NMR (CDCl ₃ , δ, ppm): 2.13 (dt, 1 H, CH—CH ₂ —CH), 2.16 (dt, 1 H, CH—CH ₂ —CH), 3.04 (m _{, 2H, CH-CHCH 2 -CS} ), 3.86 (dd, 2H, CH 2 -S), 6.17 (t, 2H, CH = CH)
¹³ C-NMR (CDCl ₃ , δ, ppm): 199.6 (C═O), 136.7 (C═C), 52.0 (C—S), 50.1 (CH—CCH ₂ —CH) ), 42.6 (CH ₂ )
_{Calcd: C 8 H 8 OS 2:} C; 52.14, H; 4.38
Found: C; 52.15, H; 0.15

(2) Synthesis of sulfur-containing compound (2- {exo-3,5-dithiatricyclo [5.5.1.0 ^2,6 ] decyl-4-one-8-sulfanyl} ethanethiol)

  A solution of α, α′-azobis (isobutyronitrile) (AIBN; 67 mg, 0.41 mmol) in dry tetrahydrofuran (THF; 8 mL) under a nitrogen atmosphere, 1,2-ethanedithiol (2.90 g, 30.30 g). 8 mmol) was added. The solution was then heated to 65 ° C., and a solution of the intermediate prepared in (1) above (3.78 g, 20.5 mmol) in dry THF (41 mL) was added dropwise via a dropping funnel. After the solution was stirred at 65 ° C. for 1 hour, the mixture was concentrated. The obtained crude product was purified by silica gel column chromatography (eluent: ether / hexane = 1/1) to obtain a white powder (yield: 2.56 g, yield: 45%).

¹ H-NMR (CDCl ₃ , δ, ppm): 1.52 (m, 1H, CH—CH ₂ —CH), 1.73 (m, 1H, SH), 1.91 (m, 2H, CHS— _{CH 2 -CH), 2.23 (m} , 1H, CHCH 2 -CH), 2.38 (m, 1H, CH 2 -CHCH 2 -CH), 2.45 (m, 1H, CHS-CHCH _{2 -CH), 2.75 (m,} 4H, CH 2 -CH 2 -SH), 2.84 (m, 1H, S-CHCH 2 -CH 2), 4.04 (d, 2H, CH-SCO -S-CH)

<Production of sulfur-containing ethylenically unsaturated group-containing compound>
Example 2
Synthesis of 2- {exo-3,5-dithiatricyclo [5.5.1.0 ^2,6 ] decyl-4-one-8-sulfanyl} ethylthiomethacrylate (compound (1-1))

  A sulfur-containing compound produced in Example 1 (1.68 g, 6.03 mmol) and phenothiazine as a polymerization initiator were placed in a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, and dry THF (65 mL) was added. To the solution was added triethylamine (2.92 g, 28.9 mmol) under a nitrogen atmosphere. The solution was then cooled to 0 ° C. and a solution of methacrylic acid chloride (2.7 g, 26.0 mmol) in dry THF (20 mL) was added dropwise via a dropping funnel. The solution was stirred at room temperature for 24 hours and then quenched with a saturated aqueous sodium bicarbonate solution. The mixture was diluted with diluted water and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography (eluent: ether / hexane = 1/3) to obtain a colorless oil (yield: 1.49 g, yield: 71%).

¹ H-NMR (CDCl ₃ , d, 25 ° C.): 1.51 (m, 1H, CH—CH ₂ —CH), 1.91 (m, 2H, CHS—CH ₂ —CH), 1.98 _{(m, 3H, CH 2 =} CCH 3), 2.22 (dd, 1H, CHCH 2 -CH), 2.44 (t, 2H, CH 2 -CHCH 2 -CHS, CHS-CHCH 2 -CHS _{), 2.71 (m, 2H,} CH 2 S-CH 2 -CHS), 2.99 (m, 1H, CH 2 S-CHCH 2 -CH), 3.12 (m, 2H, COS-CH 2 _{-CH 2), 4.10 (m,} 2H, S-CHCH-CHCH-S), 5.63 (m, 1H, CH 2 = CCH 3), 6.08 (s, 1H, CH 2 = CCH 3 )

<Manufacture of polymer>
Example 3
AIBN as a radical polymerization initiator was added to a chloroform solution (0.5 mol / L) of the compound (1-1) synthesized in Example 2 and radical polymerization was performed to produce a polymer. The polymerization proceeded smoothly and a white powder was obtained (sulfur content: 37% by weight). The obtained polymer was dissolved in chloroform, tetrachloromethane and chlorobenzene.

Example 4
A polymer was obtained in the same manner as in Example 3 except that the concentration of the chloroform solution of the compound (1-1) synthesized in Example 2 was changed to 1.0 mol / L.

Table 1 shows the molecular weights and yields of the polymers obtained in Examples 3 and 4.

  From the results in Table 1, it can be seen that if the concentration of the monomer (compound (1-1)) is high, a polymer having a higher molecular weight can be obtained.

<Characteristic evaluation of polymer film>
A polymer film was prepared by spin coating the hot cyclohexanone solution of the polymer obtained in Example 3 on a quartz substrate. The following characteristics were evaluated about the obtained polymer film.

(1) Transmittance (%)
Using a U-3500 type self-recording spectrophotometer manufactured by Hitachi, Ltd., the transmittance (%) of the cured film obtained above was measured. The UV-visible transmittance spectrum of the obtained polymer film is shown in FIG. The obtained polymer film had a high sulfur content, so the transparency was low near 350 nm, but it was excellent in the visible region (> 360 nm) (transmittance> 90%). This high transparency is considered to be due to a molecular structure having almost no π-bond having absorption in the visible region.

(2) Measurement of Refractive Index (n _D ²⁵ ) The refractive index at a wavelength of 589 nm at 25 ° C. was measured using an Atago Co., Ltd. Abbe refractometer according to JIS K7105, and it was 1.640.

(3) Measurement of Abbe number ν The refractive indices of the F-line (486 nm) and C-line (656 nm) obtained with a multi-wavelength Abbe refractometer manufactured by Atago Co., Ltd. were 1.651 and 1.636, respectively. It was 42.1 when Abbe's number was computed combining these and the refractive index of the said D line.

The novel sulfur-containing compound of the present invention can give a high refractive index and a high Abbe number to a sulfur-containing ethylenically unsaturated group-containing compound produced using this as a raw material.
The novel sulfur-containing ethylenically unsaturated group-containing compound of the present invention is suitable as a material for producing an optical member that requires a high refractive index and a high Abbe number at the same time. Specifically, examples of the optical member include a coating material of a high refractive index material and a high refractive index material of an antireflection film, an optical waveguide, various lenses, and a sensitivity improving material for an image sensor. In particular, such as lens parts of various lens sheets such as prism lens sheets used for backlights of liquid crystal display devices and lens sheets used for screens of projection televisions (for example, Fresnel lens sheets, lenticular lens sheets, etc.) It is useful as a material for optical members.

4 is a graph showing a UV-visible transmittance spectrum of the polymer film obtained in Example 3. FIG.

Claims (5)

A sulfur-containing compound represented by the following formula (1).

  A sulfur-containing ethylenically unsaturated group-containing compound obtained by reacting the sulfur-containing compound according to claim 1 with a compound having an ethylenically unsaturated group.   The sulfur-containing ethylenically unsaturated group-containing compound according to claim 2, wherein the ethylenically unsaturated group is a (meth) acryloyl group. The sulfur-containing ethylenically unsaturated group-containing compound according to claim 2 or 3, selected from the group consisting of compounds represented by the following formula (1-1).

(In the formula, R represents hydrogen or a methyl group.) The polymer obtained by polymerizing the sulfur-containing ethylenically unsaturated group containing compound of any one of Claims 2-4.

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