JPS63175834A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPS63175834A JPS63175834A JP606587A JP606587A JPS63175834A JP S63175834 A JPS63175834 A JP S63175834A JP 606587 A JP606587 A JP 606587A JP 606587 A JP606587 A JP 606587A JP S63175834 A JPS63175834 A JP S63175834A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- optical material
- organic
- group
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 150000002148 esters Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical group 0.000 claims description 21
- 125000000962 organic group Chemical group 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical group CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- -1 carboxylic acid chlorides Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、各種光素子への応用が可能な有機非線形光学
材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organic nonlinear optical material that can be applied to various optical devices.
非線形光学材料は、第二高調波発生（以下、ＢＨＧと略
す）、第三高調波発生（以下、ＴＨＧと略す）等、光の
周波数を変換する機能を有している他、これらの特性を
生かした光スィッチ、光メモリへの応用が可能であるた
め、将来の光素子の中心素材として、活発な研究開発が
進められている。なかでも、有機非線形光学材料は従来
の無機強誘電体結晶に比べ、非線形光学定数が大きいこ
と、応答が速いとと々どの特長があるので、将来の光素
子の実用化を目脂して幅広い材料探索が行われている。Nonlinear optical materials have functions such as second harmonic generation (hereinafter abbreviated as BHG) and third harmonic generation (hereinafter abbreviated as THG), as well as functions to convert the frequency of light. Because it can be applied to optical switches and optical memories, active research and development is underway to use it as a core material for future optical devices. Among them, organic nonlinear optical materials have many advantages such as large nonlinear optical constants and fast response compared to conventional inorganic ferroelectric crystals, so they are used in a wide range of applications with the aim of practical application of optical devices in the future. Material exploration is underway.
しかしながら、これらの有機材料を用いた各種素子を素
子化するに当っては、大型結晶の育成あるいは薄膜結晶
化などが必要であり、これらの結晶が得られた場合でも
、結晶の機械的強度が劣る、あるいは加工性が悪いなど
の欠点を有している。However, in order to fabricate various devices using these organic materials, it is necessary to grow large crystals or thin film crystallization, and even when these crystals are obtained, the mechanical strength of the crystals is insufficient. It has disadvantages such as being inferior or having poor workability.
これらの欠点を克服するために、ポリマー中への非線形
光学材料の分散などの方法があるが、ポリマーとの相溶
性の問題があシ、効率のよい非線形光学材料を高濃度に
分散配合することは難しい。かつこのようにして得られ
たポリマー系材料は非線形光学材料として、効率の良い
材料とは言えず、経時的に安定した特性を有しないのが
現状である。To overcome these drawbacks, there are methods such as dispersing nonlinear optical materials in polymers, but there are problems with compatibility with the polymers, so it is necessary to disperse and blend efficient nonlinear optical materials at high concentrations. is difficult. In addition, the polymer material obtained in this manner cannot be said to be an efficient material as a nonlinear optical material, and currently does not have stable characteristics over time.
本発明の目的は、上記従来技術の欠点を克服し、成型性
に優れかつ機械的強度に優れた高効率の非線形光学材料
を提供することＫある。An object of the present invention is to overcome the drawbacks of the prior art described above and provide a highly efficient nonlinear optical material that has excellent moldability and mechanical strength.
本発明を概説すれば、本発明はいずれも有機非線形光学
材料に関する発明であって、その第１の発明は、不飽和
のカルボン酸エステルのエステル部位に、下記一般式■
：
０２Ｎ−Ｚ＊ −Ｘ＝Ｙ−Ｚ２−ＨＲｌｋ
” ” ” ＣＩ）（式中Ｚ２は同一又及びＺ２は同
一又は異なり、π電子共役系の２価の環状基、Ｘ及びＹ
は同一又は異なり、Ｃａ又はＮ、Ｒ，及び鳥は同一又は
異なり、水素又は有機基を示すが、ＲＭ及びＲ２の少な
くとも一方は反応性の官能基を有する有機基である）で
表される化合物が結合した単量体であることを特徴とす
る。To summarize the present invention, all of the present inventions relate to organic nonlinear optical materials, and the first invention is based on the following general formula
: 02N-Z*-X=Y-Z2-HRlk
""" CI) (in the formula, Z2 is the same or Z2 is the same or different, a divalent cyclic group of a π-electron conjugated system, X and Y
are the same or different, Ca or N, R, and Bird are the same or different and represent hydrogen or an organic group, and at least one of RM and R2 is an organic group having a reactive functional group). It is characterized in that it is a monomer bound to.
第２の発明は、上記第１の発明の有機非線形光学材料の
単独重合体、あるいは該有機非線形光学材料とアクリル
酸エステル、メタクリル酸エステル及びスチレンよりな
る群から選択した少なくとも１種の単量体との共重合体
であることを特徴とする。A second invention is a homopolymer of the organic nonlinear optical material of the first invention, or a combination of the organic nonlinear optical material and at least one monomer selected from the group consisting of acrylic esters, methacrylic esters, and styrene. It is characterized by being a copolymer with.
また、第３の発明は、前記第１の発明の有機非線形光学
材料と、ポリアクリル酸エステル、ポリメタクリル酸エ
ステル、ポリスチレンあるいはそれらの共重合体とのグ
ラフト重合体であることを特徴とする。Further, a third invention is characterized in that it is a graft polymer of the organic nonlinear optical material of the first invention and polyacrylic ester, polymethacrylic ester, polystyrene, or a copolymer thereof.
更に、第４の発明は、前記一般式Ｉで表される化合物と
反応性を有するポリマーの側鎖に、該式■で表される化
合物が導入されたポリマーであることを特徴とする。Furthermore, the fourth invention is characterized in that the polymer has a compound represented by the formula (1) introduced into the side chain of the polymer that is reactive with the compound represented by the general formula (1).
本発明による非線形光学材料の主要な特徴は非線形光学
材料自身が重合能を有すること、及びこの重合性非線形
光学材料の重合物が非線形光学効果が高くかつ成型性、
機械的強度に優れている点である。これは効率のよい非
線形光学材料を高濃度に分散配合することは難しいとい
う従来技術の欠点を非線形光学効果が高い重合性非線形
光学材料の設計と合成及びそのポリマー化によって解決
したものである。The main features of the nonlinear optical material according to the present invention are that the nonlinear optical material itself has polymerization ability, and that the polymer of this polymerizable nonlinear optical material has a high nonlinear optical effect and moldability.
It has excellent mechanical strength. This method solves the drawback of the conventional technology that it is difficult to disperse and blend efficient nonlinear optical materials at high concentrations by designing and synthesizing polymerizable nonlinear optical materials with high nonlinear optical effects and polymerizing them.
本発明でいう重合能を有する非線形光学材料とは、例え
ばアクリル酸エステルあるいはメタクリル酸エステル等
の不飽和のカルボン酸エステルのエステル部位に次式■
〜■で表される化合物が結合した化合物群をさす。なお
、各式に′おいて、符号” ％ ｚｔ 、Ｒ１及び鳥は
前記式！と同義である。The nonlinear optical material having polymerizability as used in the present invention refers to the following formula
Refers to a group of compounds in which compounds represented by ~■ are combined. In each formula, the symbols "% zt", R1, and bird have the same meanings as in the above formula!.
０２ Ｎ −Ｚ＠ −ＣＨ＝ ＣＨ−Ｚ２−Ｎ Ｒ＋Ｂ
−２’ ” ’ （Ｉｆ ）Ｏ２Ｎ−Ｚ、−Ｎ ＝ Ｎ
−Ｚ、−ＨＲ，Ｒ，−−−（ｍ〕ｏ、Ｈ−ｚ、−ｃＨ
ｚ Ｎ −Ｚ、−ＮＲＩＲ，−−−（ｔｖ〕０、Ｈ−Ｚ
、−Ｎ ＝ＣＨ−Ｚ、−ＮＲ，Ｒ２−＊５（Ｖ）ｚｌ及
びＺ２は同一又はベンゼン環、ピリジン環、ピリミジン
環、フラン環、チアゾール環、オキサゾール環、オキサ
ジアゾール環、ナフタレン環などのπ電子共役系の２価
の環状基で、互いに等しい構造であっても、相異なる構
造であってもよい。これらの化合物はアクリル酸クロリ
ドあるいはメタクリル酸クロリド等の不飽和カルボン酸
クロリドと式■〜Ｖで表される化合物でＲ，、Ｒ２の少
なくとも一方がヒドロキシル基、アミン基、メルカプチ
ル基等を有する化合物の付加反応によって合成されるの
が一般的であるが、なかにはこの反応によシ、式■〜Ｖ
で表される化合物の中央のａｘＣ，Ｏ−Ｎ、Ｎ＝Ｎ結合
が影響を受けるため、この径路では合成されないも 。02 N -Z@ -CH= CH-Z2-N R+B
-2'''' (If )O2N-Z, -N = N
-Z, -HR,R,---(m]o, H-z, -cH
z N -Z, -NRIR, --- (tv] 0, H-Z
, -N=CH-Z, -NR, R2-*5(V) zl and Z2 are the same or a benzene ring, pyridine ring, pyrimidine ring, furan ring, thiazole ring, oxazole ring, oxadiazole ring, naphthalene ring, etc. are divalent cyclic groups having a π-electron conjugated system, which may have the same structure or different structures. These compounds include unsaturated carboxylic acid chlorides such as acrylic acid chloride or methacrylic acid chloride, and compounds represented by formulas 1 to V, in which at least one of R, R2 has a hydroxyl group, amine group, mercaptyl group, etc. Although it is generally synthesized by an addition reaction, some compounds are synthesized by this reaction.
Since the central axC, O-N, and N=N bonds of the compound represented by are affected, it cannot be synthesized by this route.
のもある。この場合は、アクリル酸クロリドあるいはメ
タクリル酸クロリドとの反応の後、縮合反応等によって
、Ｃ！−０，Ｃ＝Ｎ、Ｎ＝Ｎ結合で左右を結ぶ合成径路
をとる必要があるー。また、本発明でいう重合能を有す
る非線形光学効果を有する分子の１部分となっている式
■〜Ｖで表される化合物は従来二次の非線形光学材料と
して一部検討されてはいるが、本発明において力点をお
く三次非線形光学材料としては、これまで検討された例
はない。There is also one. In this case, after reaction with acrylic acid chloride or methacrylic acid chloride, C! It is necessary to take a composite route that connects the left and right sides with -0, C=N, and N=N connections. In addition, although the compounds represented by formulas (1) to (V), which are part of the molecule having a nonlinear optical effect and having polymerization ability in the present invention, have been partially studied as second-order nonlinear optical materials, There has been no example studied so far as the third-order nonlinear optical material, which is the focus of the present invention.
本重合性化合物は、単独で重合あるいは他のモノマーと
の共重合あるいは各種ポリマーへのグラフト重合が可能
である。いずれの場合においても、アゾビスイソブチロ
ニトリル（以下、ＡよりＮと略記する）のようなラジカ
ル開始剤によって簡単に重合する。単独重合あるいは共
重合あるいはグラフト重合、いずれの方法によって得ら
れた重合物もキャストあるいはホットプレス等によシ簡
単にフィルム状に成型できる。This polymerizable compound can be polymerized alone, copolymerized with other monomers, or graft-polymerized to various polymers. In either case, polymerization is easily carried out using a radical initiator such as azobisisobutyronitrile (hereinafter abbreviated as N rather than A). Polymers obtained by any method, such as homopolymerization, copolymerization, or graft polymerization, can be easily formed into a film by casting, hot pressing, or the like.
機械的な特性は、得られる重合物の分子量や弐■〜Ｖで
表される化合物の重合物に占める重量分率に依存する。The mechanical properties depend on the molecular weight of the resulting polymer and the weight fraction of the compounds represented by 2--V in the polymer.
また、この重量分率が大きいほど非線形光学効果は大き
くなる。重合方法としては、ＡよりＮを開始剤とするラ
ジカル反応による溶液重合が一般的な、方法として可能
であるが、本発明は重合方法について限定するものでは
ない。Moreover, the larger this weight fraction is, the larger the nonlinear optical effect becomes. As a polymerization method, solution polymerization by a radical reaction using A to N as an initiator is generally possible, but the present invention is not limited to the polymerization method.
本発明においては、上記重合能を有する非線形光学材料
の重合反応によらず、式■〜Ｖで表される化合物と反応
性を有するポリマーが反応し式■〜■で表される化合物
がポリマーの側鎖に導入されて得られるポリマーも本発
明に包含される。例えば式■〜Ｖ中の馬、馬がヒドロキ
シル基を有するとき、これらの化合物中のヒドロキシル
基と反応性を有するポリマー、例えばポリアクリル酸ク
ロリドあるいはポリメタクリル酸クロリドあるいはクロ
ルメチル化ポリスチレンあるいはこれらの共重合体と反
応し式■〜Ｖで表される化合物がポリマーの側鎖に導入
される。このように、高分子反応で得られたポリマーも
、上記の重合で得られたポリマーと同様に、成型が容易
で、模様的特性に優れた非線形光学材料になる。ただし
、この方法によって導入される式■〜■で表される化合
物の重量分率はかなり制限されるため、それだけ非線形
光学特性にも限界がある。すなわち、非線形光学特性に
関して言えば、高分子反応で得られる重合物よりも上記
重合能を有する非線形光学材料の重合によって得られる
重合物のほうが愛れている。In the present invention, regardless of the polymerization reaction of the nonlinear optical material having the above-mentioned polymerization ability, the compounds represented by formulas (1) to (5) react with the reactive polymer, and the compounds represented by formulas (1) to (5) react with the polymer. Polymers obtained by introducing side chains are also included in the present invention. For example, when the horse or horse in formulas ① to V has a hydroxyl group, a polymer that is reactive with the hydroxyl group in these compounds, such as polyacrylic acid chloride, polymethacrylic acid chloride, chloromethylated polystyrene, or a copolymer thereof. By reacting with the coalescence, compounds represented by formulas (1) to (V) are introduced into the side chains of the polymer. In this way, the polymer obtained by polymer reaction is also a nonlinear optical material that is easy to mold and has excellent pattern characteristics, similar to the polymer obtained by the above-mentioned polymerization. However, since the weight fraction of the compounds represented by formulas (1) to (4) introduced by this method is considerably limited, the nonlinear optical properties are also limited accordingly. That is, in terms of nonlinear optical properties, polymers obtained by polymerization of nonlinear optical materials having the above-mentioned polymerization ability are more popular than polymers obtained by polymer reactions.
以下、本発明材料に使用する単量体又はボリマーの製造
例を示すが、本発明はこれらに限定されない。Examples of producing monomers or polymers used in the material of the present invention will be shown below, but the present invention is not limited thereto.
製造例１
４−ニトロ−４’−（Ｎ−エチル−Ｎ−（２−ヒドロキ
シエチル）アミン〕アゾベンゼン５ｆをジオキサン１５
０７！に溶解し、これに触媒として（Ｌ４−のキノリン
を加えた。この溶液にアクリル酸クロリド０．４ｍｊを
水冷下滴下し、後室温で１８時間反応させた。反応終了
後、不溶物を除き、これに水を加えて生じる沈殿をｐ過
した。を過物をシクロヘキサンにより再結晶して、上記
式■の単量体を得た。Production Example 1 4-nitro-4'-(N-ethyl-N-(2-hydroxyethyl)amine) azobenzene 5f was mixed with dioxane 15
07! To this was added quinoline (L4-) as a catalyst. To this solution, 0.4 mj of acrylic acid chloride was added dropwise under water cooling, and the reaction was then allowed to proceed at room temperature for 18 hours. After the completion of the reaction, insoluble matter was removed, Water was added to this and the resulting precipitate was filtered.The filtered product was recrystallized from cyclohexane to obtain the monomer of the above formula (2).
製造例２
製造例１において、式Ｉに相当する化合物として、４−
ニトロ−ａｌ−（Ｎ−メチル−Ｎ−（２−ヒドロキシエ
チル）アミノ〕スチルベンヲ用い、アクリル酸クロリド
の代シにメタクリル酸クロリドを用いて同様な反応操作
を行って、上記式■の単量体を得た。Production Example 2 In Production Example 1, as a compound corresponding to formula I, 4-
A similar reaction operation was carried out using nitro-al-(N-methyl-N-(2-hydroxyethyl)amino)stilbene and methacrylic acid chloride in place of acrylic acid chloride to obtain the monomer of the formula (1) above. I got it.
製造例５ ０Ｈ。Manufacturing example 5 0H.
脱水乾燥したジオキサン７０ｒｎｌにメチルメタクリレ
−）４．５Ｐ、４−ニトロ−ａｌ −（Ｎ−エチル−Ｎ
−（２−アクリロイルオキシエチル）アミノコアゾベン
ゼン（Ｍ） ｔ ５ｙ 及ＯＡよりＮＯ，１４ｆを溶解
させ、完全に脱気した後、容器を封管した。これを６０
℃、２４時間反応させた後、反応生成物を石油エーテル
に注ぎ、沈殿させた。メタノールで洗浄後、乾燥して、
上記式■の重合体を得た。その生成は、工Ｒ１及びＮＭ
Ｒ各スペクトルによシ確認した。Methyl methacrylate) 4.5P, 4-nitro-al-(N-ethyl-N
-(2-Acryloyloxyethyl)aminocoazobenzene (M) t 5y and OA were used to dissolve NO, 14f, and after complete degassing, the container was sealed. This is 60
After reacting at ℃ for 24 hours, the reaction product was poured into petroleum ether and precipitated. After washing with methanol and drying,
A polymer of the above formula (2) was obtained. Its generation is based on engineering R1 and NM
R was confirmed by each spectrum.
製造例４
ｃｏｏｃａ３ ｃｏｃｚ
Ｃ馬
メチルメタクリレートとメタクリル酸クロリドの１＝１
共重合体５ｆを１００−のジオキサンに溶解させ、これ
にキノリン１ｄ及び４−二トローａ／ ＋ （Ｎ−メチ
ル−Ｎ−（２−ヒドロキシエチル）アミノコスチルベン
１．５りを加工、６０℃で１０時間反応させた。生成物
を石油エーテルに注ぎ、生じた沈殿をメタノールで十分
洗浄して、上記式■の重合体を得た。その生成は、工Ｒ
，，ＮＭＲ各スペクトルにより確認した。Production example 4 cooca3 cocz C 1=1 of methyl methacrylate and methacrylic acid chloride
Copolymer 5f was dissolved in 100-dioxane, and quinoline 1d and 4-nitroa/+ (N-methyl-N-(2-hydroxyethyl)aminocostilbene 1.5%) were dissolved at 60°C. The product was poured into petroleum ether, and the resulting precipitate was thoroughly washed with methanol to obtain a polymer of the above formula (2).
, , Confirmed by NMR spectra.
製造例５
製造例３におけるメチルメタクリレートの代りにスチレ
ンを用いて同様な反応操作を行って、上記式Ｘの重合体
を得た。Production Example 5 The same reaction procedure as in Production Example 3 was carried out using styrene instead of methyl methacrylate to obtain a polymer of formula X above.
製造例６
Ｃ馬
末端にメタクリレート基を有するポリスチレン〔サート
マー社製、ケムリンク（Ｏｈｓｍｌｉｎｋ ）（登録商
標名）４５００）５ｆと、４−ニトロ−ａｌ −（Ｎ−
メチル−Ｎ−（２−メタクリロイルオキシエチル）アミ
ノコスチルベン（■）ｔＳｔをベンゼン６０−に溶解さ
せ、これにＡよりＮ１１１Ｆを加え、完全に脱気した後
、容器を封管した。これを７０℃で８時間反応させ、反
応生成物を石油エーテルに注ぎ沈殿させた。その後、未
反応モノマーは熱エタノールに溶解させて除去して、上
記式Ｘの重合体を得た。Production Example 6 Polystyrene having a methacrylate group at the C-terminus (manufactured by Sartomer, Chemlink (registered trademark) 4500) 5f and 4-nitro-al-(N-
Methyl-N-(2-methacryloyloxyethyl)aminocostilbene (■)tSt was dissolved in benzene 60-, and N111F was added thereto from A, and after completely degassing, the container was sealed. This was reacted at 70° C. for 8 hours, and the reaction product was poured into petroleum ether to precipitate it. Thereafter, unreacted monomers were removed by dissolving them in hot ethanol to obtain a polymer of formula X above.
以下、実施例に基づき本発明を更に具体的に説明するが
、本発明はこれら実施例に限定されない。EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
実施例１及び２
重合能を有する有機非線形光学材料として、前記製造例
１及び２で得た構造式■及び■で表される材料の非線形
光学特性（ＴＨＧ及びＥＩＨＧ強度）を測定した。Examples 1 and 2 As organic nonlinear optical materials having polymerization ability, the nonlinear optical properties (THG and EIHG intensities) of the materials represented by the structural formulas (1) and (2) obtained in Production Examples 1 and 2 were measured.
ＴＨＧ強度は１゜９μ惜を、ＳＨＧ強度は１．０６μ倶
を基本波として、共に粉末法（Ｓ、Ｌクルッ（Ｓ、ＬＫ
ｕｒｚ）ら、ジャーナル オブ アプライド フィツク
ス（、Ｔ、 Ａｐｐｌ、 Ｐｈｙｓ、 ）第３９巻、第
３７９８頁（１９６８）参照〕により得られた値である
。The THG intensity was set at 1°9μ, and the SHG intensity was set at 1.06μ.
urz et al., Journal of Applied Physics, Vol. 39, p. 3798 (1968)].
各結果を、下記表１に示す。The results are shown in Table 1 below.
表 １
表１から明らかなように、本発明の材料は、いずれも高
いＴＵＧ強度を示した。一方、８１０強度はウレア以下
であり非常に小さい。すなわち、この材料は二次非線形
光学効果が小さく、大きな三次非線形光学効果を有する
という特徴がある。Table 1 As is clear from Table 1, all the materials of the present invention exhibited high TUG strength. On the other hand, the 810 strength is lower than urea and is very small. That is, this material is characterized by having a small second-order nonlinear optical effect and a large third-order nonlinear optical effect.
実施例５〜６
ポリマー系の有機非線形光学材料として、前記製造例３
〜６で得た構造式■〜Ｘで表される材料の非線形光学定
数χ（３） を測定した。Examples 5 to 6 As a polymer-based organic nonlinear optical material, the above Production Example 3
The nonlinear optical constant χ(3) of the materials represented by the structural formulas 1 to 6 obtained in steps 1 to 6 was measured.
この値は、１．９μ情を基本波としてフィルム状試料を
用いたＴＨＧメーカフリンジ法により求めた（ Ｆ、カ
ジャール（Ｆ、にａｉｊａｒ）ら、フィジカルリビュー
Ａ （Ｐｈｙｓ、 Ｒｅｖ、 Ａ）第３２巻、第２３５
２頁（１９８５）参照〕。標準物質はａｓ、（χ（３ン
＝１、７８ Ｘ １０−１３ｅｓｕ ）とし、た（Ｂ、
？、レバイン（Ｂ、 Ｆ、 Ｌｅｖｉｎθ）ら、ジャー
ナル オブ ケミカル フィツクス（Ｊ、 Ｏｈｅｍ、
Ｐｈｙｓ、 ）第６３巻、第２６６６頁（１９７５）
参照〕。各結果を比較例と共に下記表２に示す。This value was determined by the THG manufacturer fringe method using a film sample with 1.9μ as the fundamental wave (F, Aijar et al., Physical Review A (Phys, Rev, A), Vol. 32). , No. 235
2 (1985)]. The standard material was as, (χ (3 = 1, 78 x 10-13 esu), (B,
? , Levin (B, F, Levinθ) et al., Journal of Chemical Fixtures (J, Ohem,
Phys, ) Volume 63, Page 2666 (1975)
reference〕. The results are shown in Table 2 below along with comparative examples.
表 ２
表２から明らかなように、本発明の材料は、代表的な無
機非線形光学材料であるＬｉＮ’ｂＯ，より１桁大きく
なっている。Table 2 As is clear from Table 2, the material of the present invention is one order of magnitude larger than LiN'bO, which is a typical inorganic nonlinear optical material.
以上説明したように、本発明の有機非線形光学材料は、
いずれも三次非線形光学効果が太きいという特長がある
。また、本発明による重合能を有する有機非線形光学材
料は、成型加工性や機械的強度に優れる有機非線形光学
材料を合成する際の原料として利用できる。これを原料
としたポリマー系の材料は、三次非線形光学効果が大き
いこと、簡単にフィルム状等に成型できることなどの長
所を有するので、三次非線形光学効果を利用した光学素
子、例えば光双安定性素子、光スィッチ、光メモリなど
将来の光通信用光集積素子の中心素材として大いに利用
できる。As explained above, the organic nonlinear optical material of the present invention is
Both have the feature of having a strong third-order nonlinear optical effect. Further, the organic nonlinear optical material having polymerization ability according to the present invention can be used as a raw material for synthesizing an organic nonlinear optical material having excellent moldability and mechanical strength. Polymer-based materials made from this material have advantages such as a large third-order nonlinear optical effect and the ability to be easily formed into films, etc., so they can be used to create optical elements that utilize the third-order nonlinear optical effect, such as optical bistable elements. It can be widely used as a core material for future optical integrated devices for optical communication such as optical switches, optical memories, etc.
特許出願人 日本電信電話株式会社 同 東し株式会社Patent applicant: Nippon Telegraph and Telephone Corporation Toshi Co., Ltd.
Claims (1)
記一般式 I ： Ｏ＿２Ｎ−Ｚ＿１−Ｘ＝Ｙ−Ｚ＿２−ＮＲ＿１Ｒ＿２・
・・〔 I 〕（式中Ｚ＿１及びＺ＿２は同一又は異なり
、π電子共役系の２価の環状基、Ｘ及びＹは同一又は異
なり、ＣＨ又はＮ、Ｒ＿１及びＲ＿２は同一又は異なり
、水素又は有機基を示すが、Ｒ＿１及びＲ＿２の少なく
とも一方は反応性の官能基を有する有機基である）で表
される化合物が結合した単量体であることを特徴とする
有機非線形光学材料。 ２、不飽和のカルボン酸エステルのエステル部位に、下
記一般式 I ： Ｏ＿２Ｎ−Ｚ＿１−Ｘ＝Ｙ−Ｚ＿２−ＮＲ＿１Ｒ＿２・
・・〔 I 〕（式中Ｚ＿１及びＺ＿２は同一又は異なり
、π電子共役系の２価の環状基、Ｘ及びＹは同一又は異
なり、ＣＨ又は、Ｒ＿１及びＲ＿２は同一又は異なり、
水素又は有機基を示すが、Ｒ＿１及びＲ＿２の少なくと
も一方は反応性の官能基を有する有機基である）で表さ
れる化合物が結合した単量体である有機非線形光学材料
の単独重合体、あるいは該有機非線形光学材料とアクリ
ル酸エステル、メタクリル酸エステル及びスチレンより
なる群から選択した少なくとも１種の単量体との共重合
体であることを特徴とする有機非線形光学材料。 ３、不飽和のカルボン酸エステルのエステル部位に、下
記一般式 I ： Ｏ＿２Ｎ−Ｚ＿１−Ｘ＝Ｙ−Ｚ＿２−ＮＲ＿１Ｒ＿２・
・・〔 I 〕（式中Ｚ＿１及びＺ＿２は同一又は異なり
、π電子共役系の２価の環状基、Ｘ及びＹは同一又は異
なり、ＣＨ又はＮ、Ｒ＿１及びＲ＿２は同一又は異なり
、水素又は有機基を示すが、Ｒ＿１及びＲ＿２の少なく
とも一方は反応性の官能基を有する有機基である）で表
される化合物が結合した単量体である有機非線形光学材
料と、ポリアクリル酸、エステル、ポリメタクリル酸エ
ステル、ポリスチレンあるいはそれらの共重合体とのグ
ラフト重合体であることを特徴とする有機非線形光学材
料。 ４、下記一般式 I ： Ｏ＿２Ｎ−Ｚ＿１−Ｘ＝Ｙ−Ｚ＿２−ＮＲ＿１Ｒ＿２・
・・〔 I 〕（式中ｚ＿１及びＺ＿２は同一又は異なり
、π電子共役系の２価の環状基、Ｘ及びＹは同一又は異
なり、ＣＨ又はＮ、Ｒ＿１及びＲ＿２は同一又は異なり
、水素又は有機基を示すが、Ｒ＿１及びＲ＿２の少なく
とも一方は反応性の官能基を有する有機基である）で表
される化合物と反応性を有するポリマーの側鎖に、該式
I で表される化合物が導入されたポリマーであること
を特徴とする有機非線形光学材料。[Claims] 1. The following general formula I: O_2N-Z_1-X=Y-Z_2-NR_1R_2.
... [I] (in the formula, Z_1 and Z_2 are the same or different, a divalent cyclic group of a π-electron conjugated system, X and Y are the same or different, CH or N, R_1 and R_2 are the same or different, hydrogen or organic 1. An organic nonlinear optical material characterized in that it is a monomer bound to a compound represented by R_1 and R_2, in which at least one of R_1 and R_2 is an organic group having a reactive functional group. 2. The following general formula I: O_2N-Z_1-X=Y-Z_2-NR_1R_2・
... [I] (in the formula, Z_1 and Z_2 are the same or different, a divalent cyclic group of a π-electron conjugated system, X and Y are the same or different, CH or R_1 and R_2 are the same or different,
A homopolymer of an organic nonlinear optical material, which is a monomer bound to a compound represented by hydrogen or an organic group, in which at least one of R_1 and R_2 is an organic group having a reactive functional group, or An organic nonlinear optical material characterized in that it is a copolymer of the organic nonlinear optical material and at least one monomer selected from the group consisting of acrylic esters, methacrylic esters, and styrene. 3. The following general formula I: O_2N-Z_1-X=Y-Z_2-NR_1R_2・
... [I] (in the formula, Z_1 and Z_2 are the same or different, a divalent cyclic group of a π-electron conjugated system, X and Y are the same or different, CH or N, R_1 and R_2 are the same or different, hydrogen or organic (wherein at least one of R_1 and R_2 is an organic group having a reactive functional group) is bonded to an organic nonlinear optical material which is a monomer, and polyacrylic acid, ester, poly An organic nonlinear optical material characterized by being a graft polymer with methacrylic acid ester, polystyrene, or a copolymer thereof. 4. General formula I: O_2N-Z_1-X=Y-Z_2-NR_1R_2・
... [I] (in the formula, z_1 and Z_2 are the same or different, a divalent cyclic group of a π-electron conjugated system, X and Y are the same or different, CH or N, R_1 and R_2 are the same or different, hydrogen or organic (wherein at least one of R_1 and R_2 is an organic group having a reactive functional group) is added to the side chain of the polymer that is reactive with the compound represented by the formula
An organic nonlinear optical material characterized by being a polymer into which a compound represented by I is introduced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62006065A JPH07117671B2 (en) | 1987-01-16 | 1987-01-16 | Organic nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62006065A JPH07117671B2 (en) | 1987-01-16 | 1987-01-16 | Organic nonlinear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63175834A true JPS63175834A (en) | 1988-07-20 |
| JPH07117671B2 JPH07117671B2 (en) | 1995-12-18 |
Family
ID=11628181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62006065A Expired - Fee Related JPH07117671B2 (en) | 1987-01-16 | 1987-01-16 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07117671B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2657083A1 (en) * | 1990-01-15 | 1991-07-19 | Rhone Poulenc Chimie | Polyesters active in nonlinear optics and materials containing them, optical device containing them and processes for the manufacture of these compounds and materials |
| EP1764405A1 (en) * | 2005-09-20 | 2007-03-21 | Rolic AG | Functionalized photoreactive compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62235934A (en) * | 1986-04-07 | 1987-10-16 | Nippon Telegr & Teleph Corp <Ntt> | Wavelength conversion element |
-
1987
- 1987-01-16 JP JP62006065A patent/JPH07117671B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62235934A (en) * | 1986-04-07 | 1987-10-16 | Nippon Telegr & Teleph Corp <Ntt> | Wavelength conversion element |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2657083A1 (en) * | 1990-01-15 | 1991-07-19 | Rhone Poulenc Chimie | Polyesters active in nonlinear optics and materials containing them, optical device containing them and processes for the manufacture of these compounds and materials |
| EP1764405A1 (en) * | 2005-09-20 | 2007-03-21 | Rolic AG | Functionalized photoreactive compounds |
| WO2007033506A1 (en) * | 2005-09-20 | 2007-03-29 | Rolic Ag | Functionalized photoreactive compounds |
| US7959990B2 (en) | 2005-09-20 | 2011-06-14 | Rolic Ag | Functionalized photoreactive compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07117671B2 (en) | 1995-12-18 |
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