JP4905991B2 - High refractive index material with high Abbe number - Google Patents
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- 239000000463 material Substances 0.000 title description 5
- 229920000642 polymer Polymers 0.000 claims description 37
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- JFLJVRLBIZHFSU-UHFFFAOYSA-N 1,4-dithiane-2,5-dithiol Chemical compound SC1CSC(S)CS1 JFLJVRLBIZHFSU-UHFFFAOYSA-N 0.000 claims description 7
- 238000005227 gel permeation chromatography Methods 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
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- XPTSWAAZYABDPR-UHFFFAOYSA-N (5-acetyloxy-1,4-dithian-2-yl) acetate Chemical compound CC(=O)OC1CSC(OC(C)=O)CS1 XPTSWAAZYABDPR-UHFFFAOYSA-N 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YUIOPHXTILULQC-UHFFFAOYSA-N 1,4-Dithiane-2,5-diol Chemical compound OC1CSC(O)CS1 YUIOPHXTILULQC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- -1 acryloxymethyl Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
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- 230000009477 glass transition Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012701 michael addition polymerization Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZGBHDYNNBXTNMA-UHFFFAOYSA-N o-(5-ethanethioyloxy-1,4-dithian-2-yl) ethanethioate Chemical compound CC(=S)OC1CSC(OC(C)=S)CS1 ZGBHDYNNBXTNMA-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000001677 (2R,5R)-1,4-dithiane-2,5-diol Substances 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- WJVOTSBJSGBWKP-UHFFFAOYSA-N CCCS(CCSC1SCC(SC)SC1)(=O)=O Chemical compound CCCS(CCSC1SCC(SC)SC1)(=O)=O WJVOTSBJSGBWKP-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明は、高屈折率と高アッベ数を同時に有する重合体に関する。 The present invention relates to a polymer having a high refractive index and a high Abbe number simultaneously.
近年、レンズ材料として無機ガラスに代わり、軽量で耐衝撃性が高く大量生産が可能なプラスチックレンズが多く用いられるようになっている。眼鏡レンズの分野においてはプラスチックレンズの割合が９割にも達している。このような光学レンズの分野において、レンズのさらなる軽薄化を目的とし、高屈折率化が進められている。一方、重要な光学特性の一つとしてアッベ数がある。これは光の波長による屈折率差の度合いを表すものであり、アッベ数が高いほど差が小さく良いレンズであると言える。しかしながら、有機材料で屈折率とアッベ数は二律背反の関係にあり、これらを同時に向上させることは困難であった。 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.
また、プロジェクションテレビ等に使用されるフレネルレンズ、レンチキュラーレンズ等の光学レンズは、プレス法、キャスト法等の方法により製造されてきた。しかし、これらの方法では、製造時の加熱及び冷却に長時間を必要とするため、生産性が低いという問題があった。 In addition, optical lenses such as Fresnel lenses and lenticular lenses used in projection televisions have been manufactured by methods such as pressing and casting. However, these methods have a problem of low productivity because they require a long time for heating and cooling during production.
このような問題点を解決するために、近年、紫外線硬化性樹脂組成物を用いてレンズを製作することが検討されている。具体的には、レンズ形状の付いた金型と透明樹脂基板との間に紫外線硬化性樹脂組成物を流し込んだ後、透明樹脂基板の側から紫外線を照射し、該組成物を硬化させることによって、短時間でレンズを製造することができる。
近年のプロジェクションテレビやビデオプロジェクターの薄型化及び大型化に伴い、光学レンズを形成するための紫外線硬化性樹脂組成物に対して、高い屈折率を有することや、いわゆる青色抜け（画面が青みを帯びる現象）を防止することや、優れた力学特性を有することや、硬化前に適当な粘度（薄型化及び大型化に適する小さな粘度）を有すること等が要求されている。
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.
ここで、光学レンズを形成するための樹脂組成物として、例えば、特定の構造を有するジオール（ａ）と芳香族有機ポリイソシアネート（ｂ）と水酸基含有（メタ）アクリレート（ｃ）との反応物であるウレタン（メタ）アクリレート（Ａ）、該（Ａ）成分以外のエチレン性不飽和基含有化合物（Ｂ）、及び光重合開始剤（Ｃ）を含むことを特徴とする樹脂組成物が提案されている（特許文献１）。 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).
また、Ａ成分：特定の一般式で表わされるビス（アクリロキシメチル又はメタクリロキシメチル）トリシクロデカン４０〜８０重量％、Ｂ成分：ペンタエリスリトールテトラキス（β−チオプロピオネート）又はペンタエリスリトールテトラキス（チオグリコレート）１０〜５０重量％、Ｃ成分：ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート又はジビニルベンゼン１０〜４０重量％、からなる混合物を重合硬化して得た、屈折率（ＮＤ２０℃）が１．５３以上、アッベ数（νＤ２０℃）が４０以上である高アッベ数レンズ（特に、眼鏡用レンズ）が提案されている（特許文献２）。
A component: bis (acryloxymethyl or methacryloxymethyl) tricyclodecane represented by a specific general formula 40 to 80% by weight, B component: pentaerythritol tetrakis (β-thiopropionate) or pentaerythritol tetrakis ( thioglycolate) 10 to 50 wt%, C component: pentaerythritol triacrylate, trimethylolpropane triacrylate or
しかし、特許文献１、２等の技術を用いても、プロジェクションテレビ等の光学レンズに対する近年の要求、即ち、光学レンズの薄型化による高屈折率の要求と、高アッベ数の要求を共に十分満足させることは困難である。 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.
特に、プロジェクションテレビ等の光学レンズを形成するための有機系材料は、一般的に、長波長光よりも短波長光に対する屈折率が高いため、アッベ数が小さいと、長波長光（赤色）に比べ、短波長光（青色光）をより大きく屈折させ、テレビ画面で青色抜け（画面が青みを帯びる現象）が起きるという問題がある。近年主流になりつつある薄型のリアプロジェクションテレビ等においては、光源からフレネルレンズへの光の入射角が鋭角となり、短波長光がさらに顕著に屈折されるため、この青色抜けが大きな問題となっている。
尚、この青色抜けの問題を解消するためにアッベ数を大きくすると、屈折率が急に小さくなり、プロジェクションテレビ等における薄型化を実現することができなくなる。
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.
本発明は上述の問題に鑑みなされたものであり、高い屈折率と高いアッベ数とを同時に有する重合体を提供することを目的とする。 This invention is made | formed in view of the above-mentioned problem, and it aims at providing the polymer which has a high refractive index and a high Abbe number simultaneously.
上記目的を達成するため、本発明者らは鋭意研究を行い、１，４−ジチアン−２，５−ジチオールとジビニルスルホンとをマイケル付加重合させて得られる新規重合体が、高屈折率かつ高アッベ数を有することを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors have intensively studied and a novel polymer obtained by Michael addition polymerization of 1,4-dithian-2,5-dithiol and divinylsulfone has a high refractive index and a high refractive index. The inventors have found that it has an Abbe number and have completed the present invention.
即ち、本発明は下記の重合体及び重合体の製造方法を提供する。
１．下記式（１）
２． ２，５−ジメルカプト−１，４−ジチアンとジビニルスルホンとを、重合させる１に記載の重合体の製造方法。
３． 前記２，５−ジメルカプト−１，４−ジチアンが、４０モル％以上がシス異性体からなる２に記載の製造方法。
That is, this invention provides the following polymer and the manufacturing method of a polymer.
1. Following formula (1)
2. 2. The method for producing a polymer according to 1, wherein 2,5-dimercapto-1,4-dithiane and divinyl sulfone are polymerized.
3. 3. The production method according to 2, wherein the 2,5-dimercapto-1,4-dithiane comprises 40 mol% or more of a cis isomer.
本発明によれば、高屈折率と高アッベ数とを同時に有する重合体を提供することができる。
本発明によれば、透明性に優れ、高屈折率と高アッベ数とを同時に有する硬化膜を提供することができる。
According to the present invention, a polymer having a high refractive index and a high Abbe number at the same time can be provided.
According to the present invention, it is possible to provide a cured film having excellent transparency and having a high refractive index and a high Abbe number at the same time.
以下、本発明の重合体について詳細に説明する。
本発明の重合体は下記式（１）で示される構造単位を有することを特徴とする。
The polymer of the present invention is characterized by having a structural unit represented by the following formula (1).
また、本発明の重合体の製造方法（以下、本発明の製造方法という）は、２，５−ジメルカプト−１，４−ジチアン（以下、ＤＴ−ＤＴということがある）とジビニルスルホン（以下、ＤＶＳということがある）とを、マイケル付加重合させることを特徴とする。
下記に本発明の製造方法を反応式で示す。
The polymer production method of the present invention (hereinafter referred to as the production method of the present invention) includes 2,5-dimercapto-1,4-dithiane (hereinafter also referred to as DT-DT) and divinyl sulfone (hereinafter referred to as “the production method of the present invention”). DVS), and Michael addition polymerization.
The production method of the present invention is shown in the following reaction formula.
本発明の重合体の一方の原料モノマーであるＤＴ−ＤＴは公知化合物であり、その製造方法については、後述する合成例において具体的に説明する。
本発明の製造方法で用いるＤＴ−ＤＴには、シス異性体及びトランス異性体が存在し、シス−リッチなＤＴ−ＤＴを用いると、各種溶剤（熱ジメチルホフムアミド（ＤＭＦ）、Ｎ−メチル−ピロリドン（ＮＭＰ）、γ−ブチロラクトン等）に対する溶解性が高く、一方、トランス異性体のみ若しくはトランス−リッチなＤＴ−ＤＴを用いた場合には、溶剤に殆ど溶解しない（実施例１及び２を参照）。このように、ＤＴ−ＤＴのシス−トランス異性体は得られる重合体の溶剤溶解性に影響を与える。本発明の重合体から薄膜を形成する場合には、溶剤に溶解可能な塗布性に優れるシス−リッチなＤＴ−ＤＴを用いることが好ましい。
DT-DT, which is one raw material monomer of the polymer of the present invention, is a known compound, and its production method will be specifically described in the synthesis examples described later.
DT-DT used in the production method of the present invention has cis isomer and trans isomer. When cis-rich DT-DT is used, various solvents (thermal dimethylformamide (DMF), N-methyl) are used. -Pyrrolidone (NMP), γ-butyrolactone, etc.) are highly soluble. On the other hand, when only the trans isomer or trans-rich DT-DT is used, it hardly dissolves in the solvent (Examples 1 and 2). reference). Thus, the cis-trans isomer of DT-DT affects the solvent solubility of the resulting polymer. When forming a thin film from the polymer of this invention, it is preferable to use cis-rich DT-DT excellent in the applicability | paintability which can be melt | dissolved in a solvent.
ＤＴ−ＤＴのシス及びトランス異性体の割合（モル比）は、シス異性体の割合が４０モル％以上が好ましく、５０モル％以上であることがより好ましい。シス異性体の割合が上記範囲より少ないと、生成物が有機溶剤に不要化するおそれがある。 As for the ratio (molar ratio) of the cis-trans isomer of DT-DT, the ratio of the cis isomer is preferably 40 mol% or more, and more preferably 50 mol% or more. When the ratio of the cis isomer is less than the above range, the product may be unnecessary in the organic solvent.
シス−リッチなＤＴ−ＤＴを製造するには、シス及びトランスの混合物を過剰のクロロホルムに溶解させ、その後クロロホルムを減圧留去又は−４０℃まで冷却し、析出した固体（トランス体）を濾別すればよい。 In order to produce cis-rich DT-DT, a mixture of cis and trans is dissolved in excess chloroform, and then chloroform is distilled off under reduced pressure or cooled to −40 ° C., and the precipitated solid (trans form) is filtered off. do it.
他方の原料モノマーであるＤＶＳは、例えば試薬として市販されているものを使用することができる。 As the other raw material monomer DVS, for example, a commercially available reagent can be used.
ＤＴ−ＤＴとＤＶＳの重合反応の反応条件は、特に限定されないが、下記条件を用いることができる。
ジビニルスルホン（ＤＶＳ）（１ｍｍｏｌ）とＤＴ−ＤＴ（０．９〜１．１ｍｍｏｌ）を入れ、窒素置換する。脱水クロロホルムやＴＨＦ（２〜５ｍＬ）を加えて、モノマーを完全に溶解させた後、トリエチルアミン等の有機塩基を触媒量を加え、常温〜８０℃で１〜１２時間攪拌する。
The reaction conditions for the polymerization reaction of DT-DT and DVS are not particularly limited, but the following conditions can be used.
Divinyl sulfone (DVS) (1 mmol) and DT-DT (0.9 to 1.1 mmol) are added, and nitrogen substitution is performed. Dehydrated chloroform and THF (2 to 5 mL) are added to completely dissolve the monomer, and then a catalytic amount of an organic base such as triethylamine is added, followed by stirring at room temperature to 80 ° C. for 1 to 12 hours.
本発明の重合体の数平均分子量（Ｍｎ）は、１，０００〜１００，０００であることが好ましく、５，０００〜５０，０００であることがより好ましい。数平均分子量が１，０００未満であると、硬化膜が脆いおそれがあり、１００，０００を超えると、有機溶剤に不溶化するおそれがある。
数平均分子量は、ゲルパーミエーションクロマトグラフィーで測定した、ポリスチレン換算の数平均分子量を表す。
The number average molecular weight (Mn) of the polymer of the present invention is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000. If the number average molecular weight is less than 1,000, the cured film may be brittle, and if it exceeds 100,000, it may be insolubilized in an organic solvent.
The number average molecular weight represents the number average molecular weight in terms of polystyrene measured by gel permeation chromatography.
本発明の重合体の分子量分布（Ｍｗ／Ｍｎ）は、１〜２の範囲内であることが好ましく、１〜１．５の範囲内であることがより好ましい。
ここで、重量平均分子量（Ｍｗ）も、ゲルパーミエーションクロマトグラフィーによって測定する。
The molecular weight distribution (Mw / Mn) of the polymer of the present invention is preferably in the range of 1 to 2, more preferably in the range of 1 to 1.5.
Here, the weight average molecular weight (Mw) is also measured by gel permeation chromatography.
本発明の重合体を、例えば、フィルム状に成形する方法は特に制限されないが、目的とするフィルムの厚さ等に応じて適宜選択すればよい。例えば、重合体の溶剤溶液を石英基板等の基材上に塗布（キャスト）し、通常４０〜１２０℃、好ましくは８０〜１００℃の温度範囲のホットプレート上で、通常１〜５時間、好ましくは１〜２時間乾燥させた後、真空炉（Ｖａｃｕｕｍ ｏｖｅｎ）中、減圧下（圧力０．１〜０．５Torr）、通常４０〜２００℃、好ましくは８０〜１００℃の温度範囲で、通常１〜１２時間、好ましくは３〜６時間乾燥させればよい。 The method for forming the polymer of the present invention into, for example, a film is not particularly limited, and may be appropriately selected depending on the thickness of the target film. For example, a polymer solvent solution is coated (cast) on a base material such as a quartz substrate, and is usually 40 to 120 ° C., preferably 80 to 100 ° C. on a hot plate, usually 1 to 5 hours, preferably Is dried for 1 to 2 hours and then in a vacuum oven under reduced pressure (pressure 0.1 to 0.5 Torr), usually 40 to 200 ° C., preferably 80 to 100 ° C., usually 1 The drying may be performed for -12 hours, preferably 3-6 hours.
本発明の重合体は、硫黄含量が高く、優れた透明性、高屈折率と高アッベ数とを同時に有するものであるが、これらの物性については、実施例において具体的に説明する。 The polymer of the present invention has a high sulfur content and has excellent transparency, high refractive index and high Abbe number at the same time. These physical properties will be specifically described in Examples.
以下、本発明を合成例及び実施例によってさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples.
合成例１
２，５−ジアセトキシ−１，４−ジチアンの合成
Synthesis of 2,5-diacetoxy-1,4-dithiane
収量：９．９ｇ
収率：６１%
融点：１６１℃
ＩＲ（ＫＢｒ，nｃｍ−１）：２９６６，２９３５（アルキルＣ−Ｈ），１７３９（エステルＣ＝Ｏ），１４３１（アルキルＣ−Ｈ），１３６９（アセチルＣ−Ｈ），７２５（アルキルＣ−Ｈ）
１Ｈ−ＮＭＲ（ＣＤＣｌ３，δ，ｐｐｍ）：２．１８（ｔ，２Ｈ，−ＣＨ３），２．８１（ｄｄ，２Ｈ，ＣＨＯ−ＣＨ２−Ｓ），３．６９（ｄｄ，２Ｈ，ＣＨＯ−ＣＨ２−Ｓ），５．８３（ｔ，２Ｈ，Ｏ−ＣＨ（ＣＨ２）-Ｓ）
１３Ｃ−ＮＭＲ：２１．１（−ＣＨ３），２９．０（Ｓ−ＣＨ２−ＣＨＳ），６６．１（Ｓ−ＣＨ−Ｏ），１６９．７（Ｃ＝Ｏ）
元素分析：
計算値 Ｃ８Ｈ１２Ｏ４Ｓ２： Ｃ；４０．６６，Ｈ；５．１２
実測値： Ｃ；４０．７５，Ｈ；５．０４
Yield: 9.9g
Yield: 61%
Melting point: 161 ° C
IR (KBr, ncm −1 ): 2966, 2935 (alkyl C—H), 1739 (ester C═O), 1431 (alkyl C—H), 1369 (acetyl C—H), 725 (alkyl C—H)
1 H-NMR (CDCl 3 , δ, ppm): 2.18 (t, 2H, —CH 3 ), 2.81 (dd, 2H, CHO—CH 2 —S), 3.69 (dd, 2H, CHO-CH 2 -S), 5.83 (t, 2H, O-CH (CH 2) -S)
13 C-NMR: 21.1 (—CH 3 ), 29.0 (S—CH 2 —CHS), 66.1 (S—CH—O), 169.7 (C═O)
Elemental analysis:
Calculated C 8 H 12 O 4 S 2 : C; 40.66, H; 5.12
Actual value: C; 40.75, H; 5.04
合成例２
２，５−ジチオアセトキシ−１，４−ジチアンの合成
Synthesis of 2,5-dithioacetoxy-1,4-dithiane
収量：６．２９ｇ
収率：６７%
融点：１２３℃
ＩＲ（ＫＢｒ，nｃｍ−１）：２９５８，２９０４（アルキルＣ−Ｈ），１６９３（チオエステルＣ＝Ｏ），１３５３（アセチルＣ−Ｈ）
１Ｈ−ＮＭＲ（ＣＤＣｌ３，δ，ｐｐｍ）：２．３８（ｓ，６Ｈ，−ＣＨ３），２．９４（ｄｄ，１Ｈ，Ｓ−ＣＨ２−ＣＨＳ），３．１２（ｄｄ，１Ｈ，Ｓ−ＣＨ２-ＣＨＳ），３．３４（ｄｄ，１Ｈ，Ｓ−ＣＨ２−ＣＨＳ），３．６３（ｄｄ，１Ｈ，Ｓ−ＣＨ２−ＣＨＳ），４．８７（ｍ，２Ｈ，Ｓ−ＣＨ２−Ｓ）
１３Ｃ−ＮＭＲ：３０．４（−ＣＨ３，シス），３０．５（−ＣＨ３，トランス），３３．６（ＣＨ−ＣＨ２−Ｓ，トランス），３５．６（ＣＨ−ＣＨ２−Ｓ，シス），４１．９（Ｓ−ＣＨ−Ｓ，トランス），４２．６（Ｓ−ＣＨ−Ｓ，シス），１９２．８（Ｃ＝Ｏ，シス），１９３．４（Ｃ＝Ｏ，トランス）
元素分析：
計算値：Ｃ８Ｈ１２Ｏ２Ｓ４： Ｃ；３５．８，Ｈ；４．５１
実測値：Ｃ；３５．７９，Ｈ；４．３４
Yield: 6.29g
Yield: 67%
Melting point: 123 ° C
IR (KBr, ncm −1 ): 2958, 2904 (alkyl C—H), 1693 (thioester C═O), 1353 (acetyl C—H)
1 H-NMR (CDCl 3 , δ, ppm): 2.38 (s, 6H, —CH 3 ), 2.94 (dd, 1H, S—CH 2 —CHS), 3.12 (dd, 1H, S-CH 2 -CHS), 3.34 (dd, 1H, S-CH 2 -CHS), 3.63 (dd, 1H, S-CH 2 -CHS), 4.87 (m, 2H, S- CH 2 -S)
13 C-NMR: 30.4 (—CH 3 , cis), 30.5 (—CH 3 , trans), 33.6 (CH—CH 2 —S, trans), 35.6 (CH—CH 2 —) S, cis), 41.9 (S-CH-S, trans), 42.6 (S-CH-S, cis), 192.8 (C = O, cis), 193.4 (C = O, Trance)
Elemental analysis:
Calculated value: C 8 H 12 O 2 S 4 : C; 35.8, H; 4.51
Found: C; 35.79, H; 4.34
合成例３
２，５−ジメルカプト−１，４−ジチアン（ＤＴ−ＤＴ）の合成
濾液が中性になるまで水洗し、硫酸マグネシウムを用いて乾燥させ、減圧乾燥すると、黄色オイル状液体が得られる。クーゲル蒸留器を用いて、０．１２Ｔｏｒｒ／１８０℃で減圧蒸留を行い、得られた黄色結晶をクロロホルムで再結晶して、シス／トランス混合物の白色粉末を得た。
Synthesis example 3
Synthesis of 2,5-dimercapto-1,4-dithiane (DT-DT)
The filtrate is washed with water until neutral, dried with magnesium sulfate, and dried under reduced pressure to give a yellow oily liquid. Using a Kugel distiller, vacuum distillation was performed at 0.12 Torr / 180 ° C., and the resulting yellow crystals were recrystallized from chloroform to obtain a white powder of a cis / trans mixture.
収量：０．７５ｇ
収率：８%
融点：５２℃
ＩＲ（ＫＢｒ，nｃｍ−１）：２９３４，２８９７（アルキルＣ−Ｈ），２４９９（チオールＳ−Ｈ）
１Ｈ−ＮＭＲ（ＣＤＣｌ３，δ，ｐｐｍ）：２．６６（ｄ，２Ｈ，−ＳＨ（トランス）），２．７２（ｄ，２Ｈ，−ＳＨ（シス）），３．１４（ｄｄ，２Ｈ，Ｓ−ＣＨ２−ＣＨ（トランス）），３．１４（ｄｄ，２Ｈ，Ｓ−ＣＨ２−ＣＨ（シス）），３．２７（ｄｄ，２Ｈ，Ｓ−ＣＨ２−ＣＨ（トランス）），３．４１（ｄｄ，２Ｈ，Ｓ−ＣＨ２−ＣＨ（シス）），４．１０（ｔｄ，２Ｈ，ＣＨ−ＳＨ（トランス）），４．２０（ｔｄ，２Ｈ，Ｓ−ＣＨ−ＳＨ（シス））
１３Ｃ−ＮＭＲ：３８．８（Ｓ−ＣＨ２−ＣＨ），４２．４（Ｓ−ＣＨ−ＳＨ）
元素分析
計算値：Ｃ４Ｈ８Ｓ４： Ｃ；２６．０６，Ｈ；４．３７
測定値： Ｃ；２５．９５，Ｈ；４．０９
Yield: 0.75g
Yield: 8%
Melting point: 52 ° C
IR (KBr, ncm −1 ): 2934, 2897 (alkyl C—H), 2499 (thiol S—H)
1 H-NMR (CDCl 3 , δ, ppm): 2.66 (d, 2H, —SH (trans)), 2.72 (d, 2H, —SH (cis)), 3.14 (dd, 2H) , S-CH 2 -CH (trans)), 3.14 (dd, 2H , S-CH 2 -CH ( cis)), 3.27 (dd, 2H , S-CH 2 -CH ( trans)), 3.41 (dd, 2H, S—CH 2 —CH (cis)), 4.10 (td, 2 H, CH—SH (trans)), 4.20 (td, 2 H, S—CH—SH (cis) ))
13 C-NMR: 38.8 (S—CH 2 —CH), 42.4 (S—CH—SH)
Analysis Calculated: C 4 H 8 S 4: C; 26.06, H; 4.37
Measurement: C; 25.95, H; 4.09
実施例１
式（１）で示される構造単位を有する重合体（ＤＶＳ／ＤＴ−ＤＴ）の製造
Production of a polymer (DVS / DT-DT) having a structural unit represented by the formula (1)
得られた重合体は、加熱したジメチルホルムアミド（ＤＭＦ）、Ｎ−メチル−ピロリドン（ＮＭＰ）及びγ−ブチロラクトンに溶解した。
得られた重合体の硫黄含量は、計算の結果５３重量％であった。
得られた重合体のＦＴ−ＩＲチャートを図１に示す。
The obtained polymer was dissolved in heated dimethylformamide (DMF), N-methyl-pyrrolidone (NMP) and γ-butyrolactone.
The sulfur content of the polymer obtained was 53% by weight as a result of calculation.
The FT-IR chart of the obtained polymer is shown in FIG.
実施例２
式（１）で示される構造単位を有する重合体の製造
トランス−リッチなＤＴ−ＤＴ（シス：トランス＝１：２）を用いた以外は、実施例１と同様にしてＤＶＳ／ＤＴ−ＤＴを得た。
尚、トランス体のみのＤＴ−ＤＴ、若しくはトランス−リッチのＤＴ−ＤＴを用いた場合には、各種溶媒に不溶の白色固体が得られ、ＤＭＦに溶解する部分の分子量を測定すると、７０００程度であった。
Example 2
Production of polymer having structural unit represented by formula (1) DVS / DT-DT was prepared in the same manner as in Example 1 except that trans-rich DT-DT (cis: trans = 1: 2) was used. Obtained.
In addition, when using DT-DT of a trans form only or trans-rich DT-DT, a white solid insoluble in various solvents is obtained, and when the molecular weight of the portion dissolved in DMF is measured, it is about 7000. there were.
＜重合体の特性評価＞
上記実施例１で得られた重合体（ＤＶＳ／ＤＴ−ＤＴ）の下記特性を下記方法により測定した。得られた結果を表１に示す。
<Characteristic evaluation of polymer>
The following characteristics of the polymer (DVS / DT-DT) obtained in Example 1 were measured by the following method. The obtained results are shown in Table 1.
（硬化膜の調製）
実施例１で製造したＤＶＳ／ＤＴ−ＤＴ（シス−リッチ）の重合体（１１４ｍｇ）を、８０℃に加熱したＤＭＦ（２８０μＬ）に溶解させた後、テフロン（登録商標）テープを貼ったガラス基板上にキャストした。１００℃のホットプレート上で５時間乾燥させた後、真空炉（Ｖａｃｕｕｍ ｏｖｅｎ）中で、減圧下、１７０℃で３時間乾燥させると、７１０μｍ厚の、透明で自立する（フリースタンディングな）フィルムを得た。
(Preparation of cured film)
A glass substrate on which a DVS / DT-DT (cis-rich) polymer (114 mg) produced in Example 1 was dissolved in DMF (280 μL) heated to 80 ° C., and then a Teflon (registered trademark) tape was attached. Cast on top. After drying on a hot plate at 100 ° C. for 5 hours and then drying at 170 ° C. for 3 hours under reduced pressure in a vacuum oven, a transparent, free-standing (free standing) film having a thickness of 710 μm is obtained. Obtained.
（１）屈折率（ｎＤ ２５）
ＪＩＳ Ｋ７１０５に従い、（株）アタゴ製アッベ屈折計を用いて、２５℃における波長５８９ｎｍでの屈折率を測定したところ、１．６８５９であった。
(1) Refractive index (n D 25 )
In accordance with JIS K7105, the refractive index at a wavelength of 589 nm at 25 ° C. was measured using an Atago Co., Ltd. Abbe refractometer.
（２）アッベ数νの測定
（株）アタゴ製の多波長アッベ屈折計で求めた、Ｆ線（４８６ｎｍ）、Ｃ線（６５６ｎｍ）の屈折率はそれぞれ１．６９６１及び１．６８２０であった。これらと、上記Ｄ線（５８９ｎｍ）の屈折率１．６８５９と合わせてアッベ数を算出したところ、４８．６であった。
(2) 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 1.6961 and 1.6820, respectively. It was 48.6 when the Abbe number was calculated combining these and the refractive index of the said D line (589 nm) 1.68859.
（３）透過率（％）
日立製作所社製のＵ−３５００型自記分光光度計を使用して、上記で得られた硬化膜の透過率（％）をそれぞれ測定した。得られた重合体フィルムのＵＶ−可視透過率スペクトルを図２に示す。得られた重合体フィルムは硫黄含量が高いため３５０ｎｍ付近では透明性が低かったが、可視領域（＞３６０ｎｍ）では透明性に優れていた（透過率＞９０％）。この高い透明性は可視領域に吸収を有するπ−結合を殆ど有しない分子構造によると考えられる。
(3) 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.
（４）ガラス転移温度（℃）
ＤＳＣ分析により、上記で得られた硬化膜のガラス転移温度（Ｔｇ）を測定したところ、１５１℃であった。
(4) Glass transition temperature (° C)
It was 151 degreeC when the glass transition temperature (Tg) of the cured film obtained above was measured by DSC analysis.
（５）５％重量減少温度（５％ ｗｅｉｇｈｔｌｏｓｓ ｔｅｍｐｅｒａｔｕｒｅ（Ｎ２））（℃）
ＴＧＡ測定により、上記で得られた硬化膜の熱重量減少率を測定した。５％重量減少率が２７４．４℃と高い耐熱性を有することがわかる。
(5) 5% weight loss temperature (5% weightloss temperature (N 2 )) (° C.)
The thermogravimetric reduction rate of the cured film obtained above was measured by TGA measurement. It can be seen that the 5% weight reduction rate is as high as 274.4 ° C.
上記の結果から、本発明の重合体は、高い屈折率と高いアッベ数とを両立でき、かつ透明性にも優れていることがわかる。
また、シス−リッチはＤＴ−ＤＴを用いて製造された重合体は、溶剤への溶解性にも優れており、塗工も容易であることがわかる。
From the above results, it can be seen that the polymer of the present invention can achieve both a high refractive index and a high Abbe number and is excellent in transparency.
In addition, it can be seen that the polymer produced using DT-DT is excellent in solubility in a solvent and is easy to apply.
本発明の重合体は、高屈折率と高アッベ数とを同時に有しているため、高屈折率及び高アッベ数のいずれか一方又は両方が求められる分野において有用な材料となる。
本発明の重合体は、さらに透明性に優れているため、光学材料、特にプロジェクションテレビ等に使用されるフレネルレンズ、レンチキュラーレンズ等の光学レンズ材料として好適に用いることができる。
Since the polymer of the present invention has a high refractive index and a high Abbe number at the same time, it is a useful material in a field where one or both of a high refractive index and a high Abbe number are required.
Since the polymer of the present invention is further excellent in transparency, it can be suitably used as an optical material such as an optical material such as a Fresnel lens or a lenticular lens used in a projection television.
Claims (3)
The production method according to claim 2, wherein 40 mol% or more of the 2,5-dimercapto-1,4-dithiane comprises a cis isomer.
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