JPS62210432A - Non linear optical material - Google Patents
Non linear optical materialInfo
- Publication number
- JPS62210432A JPS62210432A JP5388486A JP5388486A JPS62210432A JP S62210432 A JPS62210432 A JP S62210432A JP 5388486 A JP5388486 A JP 5388486A JP 5388486 A JP5388486 A JP 5388486A JP S62210432 A JPS62210432 A JP S62210432A
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-
- 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
- G02F1/3611—Organic materials containing Nitrogen
- G02F1/3612—Heterocycles having N as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、薄膜、単結晶などのデバイスの製造に有用な
親規物質に関する。より詳しくは、本発明は電気−光学
デバイス、第２高調波発生デバイス、圧電デバイス、導
波路、および半導体など、詩に膜または層の配列体また
は集会体が構成要素として用いられるデバイスに用いる
に適し九非線形光学材料に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to parent substances useful for manufacturing devices such as thin films and single crystals. More particularly, the present invention is suitable for use in devices such as electro-optical devices, second harmonic generation devices, piezoelectric devices, waveguides, and semiconductors in which an arrangement or assembly of films or layers is used as a component. Regarding nine suitable nonlinear optical materials.
（従来の技術）
近年、非線形光学効果−強いレーザー光を物質に入射し
次時、その相互作用によって入射光と異なつ次成分を持
つ出射光が得られる現ｆ象−七有し次材料が注目を集め
ている。かかる材料は、一般に非線形光学材料として知
られており、例えば次のものなどに詳しく記載されてい
る。’ Ｎｏｎ１ｉｎｅｒＯｐｔｉｃａｌ Ｐｒｏｐ
ｅｒｔｉｅｓ ｏｆ Ｏｒｇａｎｉｃａｎｄ Ｐｏ
ｌｙｍｅｒｉｃ Ｍａｔｅｒｉａｌｓ ’人Ｃ８ＳＹＭ
ＰＯＣ８５Ｙ ５ＥＲＩＥＳ ２３ｓ、Ｄａｖｉｄ
Ｊ、Ｗｉｌｌｉａｍｓ＊（Ａｍｅｒｉｃａｎ Ｃｈｅｍ
ｉｃａｌＳｏｃｉｅｔｙ、 ｔりｔ３年刊）、「有機非
線形光学材料」加藤政雄、中西へ部監修（シー・エム・
シ−社、／りｒｒ年刊）。(Prior art) In recent years, the nonlinear optical effect - a phenomenon in which an intense laser beam is incident on a material and the next time, due to the interaction, an emitted light with a different order component from the incident light is obtained - a seven-dimensional material has been studied. It is attracting attention. Such materials are generally known as nonlinear optical materials and are described in detail in, for example: 'Nonliner Optical Prop
erties of organic and po
Lymeric Materials 'People C8SYM
POC85Y 5ERIES 23s, David
J. Williams* (American Chem
icalSociety, published in 3 years), "Organic Nonlinear Optical Materials" Masao Kato, Supervised by Nakanishihe Department (C.M.
Published by C-sha, /rirr).
非線形光学材料の用途の１つに、２次の非線形効果に基
いた第２高調波発生（ＳＨＧ）および和周波、差周波を
用い念波長変換デバイスがある。One of the applications of nonlinear optical materials is optical wavelength conversion devices using second harmonic generation (SHG) based on second-order nonlinear effects and sum frequency and difference frequency.
これまで実用上用いられているものは、ニオブ酸リチウ
ムに代表される無機質のペロブスカイト類である。しか
し近年にな夛、電子供与基および電子吸引基を有するπ
電子共役系有機化合物は前述の無機質を大きく上回る、
非線形光学材料としての諸性能を有していることが知ら
れるようになった。しかしながら、高い８ＨＧｔ示すこ
とで知られているｐ−ニトロアニリンの誘導体、例えば
、コーメチルーダーニトロアニリン（ＭＮＡ）やコーＮ
、Ｎ−ジメチルアミノー！−ニトロアセトアニリド責Ｄ
ＡＮ）などでは、強く黄色に着色している九めに、青色
光に対する透過率が低く問題となっている。従って青色
光に対する透過率の高い非線形光学材料の出現が望まれ
ている。従来、ニトロアニリンのベンゼン核の炭素原子
を窒素原子などで喧き換えることが検討されて米九が必
ずしも満足のいく結果は得られていない。The materials that have been practically used so far are inorganic perovskites represented by lithium niobate. However, in recent years, π with electron-donating and electron-withdrawing groups has become increasingly popular.
Electronically conjugated organic compounds greatly exceed the aforementioned inorganic materials.
It has become known that it has various properties as a nonlinear optical material. However, derivatives of p-nitroaniline known to exhibit high 8HGt, such as co-methyl-dernitroaniline (MNA) and co-N
, N-dimethylamino! - Nitroacetanilide D
AN), which is strongly colored yellow, has a problem of low transmittance to blue light. Therefore, the emergence of nonlinear optical materials with high transmittance for blue light is desired. In the past, attempts have been made to replace the carbon atom in the benzene nucleus of nitroaniline with a nitrogen atom, but the results have not always been satisfactory to Yonekyu.
（発明が解決しようとする問題点）
従って、本発明の目的は青色光に対する透過率の高く、
且つ高い非線形光学効果を示す新規な有機化合物を提供
することにある。(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide high transmittance for blue light;
Another object of the present invention is to provide a novel organic compound that exhibits high nonlinear optical effects.
（問題点を解決するための手段）
本発明者らは前記の目的を、従来の方法とは異り、ニト
ロアニリン骨格を保持し次ままで更にベンゼン核の炭素
原子を窒素原子などで置換することによって達成できる
ことを見出し、本発明を成すに至つ九。本発明の目的は
下記一般式（Ｉ）またはその付加物で示される化合物を
用いることによシ達成することができる。(Means for Solving the Problems) The present inventors achieved the above-mentioned objective by retaining the nitroaniline skeleton and replacing the carbon atoms of the benzene nucleus with nitrogen atoms, etc., unlike conventional methods. We discovered that this could be accomplished by doing so, and came up with the present invention. The objects of the present invention can be achieved by using a compound represented by the following general formula (I) or an adduct thereof.
一般式（Ｉ）
、−２４
式中、ｚｌは少くとも１つのニトロ基を置換基として有
する！ないし４員芳香族環を形成するに必要な原子群を
表わす。ｚ２は置換および縮環されていてもよい、ピロ
ール環、イミダゾール環、ピラゾール環、トリアゾール
環、またはテトラゾール環を形成するに必要な原子群を
表わす。General formula (I), -24 In the formula, zl has at least one nitro group as a substituent! represents an atomic group necessary to form a 4-membered aromatic ring. z2 represents an atomic group necessary to form a pyrrole ring, imidazole ring, pyrazole ring, triazole ring, or tetrazole ring, which may be substituted or fused.
上記の酸付加物とは、一般式（りの化合物に有機酸（例
えば、カルボン酸、スルホン酸など）、ま友は無機酸（
例えば、硫酸、塩酸、硝酸、リン酸など）が付加（過常
７分子）したものである。The above acid adducts are compounds with the general formula (Rin) and organic acids (e.g. carboxylic acids, sulfonic acids, etc.), and inorganic acids (
For example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) are added (usually 7 molecules).
Ｚ”Ｋよって形成される！ないしｔ員芳香族環としては
例えばチアゾール類、オキサゾール畑、イミダゾール類
、ピリジン類、ピリミジン類、ベンゼン類が挙げられ、
これらは下記の基で置換されていたり、縮環されていて
もよい。Examples of the !- or t-membered aromatic ring formed by Z"K include thiazoles, oxazoles, imidazoles, pyridines, pyrimidines, and benzenes,
These may be substituted with the following groups or may be fused.
置換基としては例えばアルキル基、アリール基、ハロゲ
ン原子、アルコキシ基、アリールオキシ基、アシルアミ
ノ基、カルバモイル基、スルファモイル基、アシルオキ
シ基、アルキルオキシカルボニル基、アリールオキシカ
ルボニル基、アルキルオキシスルホニル基、アリールオ
キシスルホニル基、アルキルチオ基、アリールチオ基、
ヒドロキシ基、チオール基、カルメキシ基、ウレイド基
、シアノ基、アルキルスルホニル基、アリールスルホニ
ル基、アルキルスルフィニル基、アリールスルフィニル
基、ニトロ基などが挙げられる。Examples of substituents include alkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, acylamino groups, carbamoyl groups, sulfamoyl groups, acyloxy groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, alkyloxysulfonyl groups, and aryloxy groups. Sulfonyl group, alkylthio group, arylthio group,
Examples include a hydroxy group, a thiol group, a carmexyl group, a ureido group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, and a nitro group.
前記アルキル基としては、例えばメチル基、エチル基、
イソプロピル基、ブチル基、ｔ−メチル基、オクチル基
、ｔ−オクチル基、デシル基、ヘキサデシル基、トコシ
ル基、コーヒドロキシェチル基、カルボキシメチル基、
シアンメチル基、コーメトキシエチル基、ベンジル基、
コーフェニルエチル基、トリフルオロメチル基、ｊ−（
Ｊ−ベンゾイミダゾリル）プロピル基などが挙げられる
。Examples of the alkyl group include methyl group, ethyl group,
Isopropyl group, butyl group, t-methyl group, octyl group, t-octyl group, decyl group, hexadecyl group, tocosyl group, co-hydroxyethyl group, carboxymethyl group,
cyanmethyl group, comethoxyethyl group, benzyl group,
Cophenylethyl group, trifluoromethyl group, j-(
Examples include J-benzimidazolyl)propyl group.
前記アリール基としてはフェニル基、グーメチルフェニ
ル基、３−メトキシフェニル基、≠−クロロフェニル基
などが挙げられる。前記ハロゲン原子としてはフッ素原
子、塩素原子、臭素原子、沃素原子が挙げられる。アル
コキシ基としては例えばメトキシ基、ブトキシ基、コー
メトキシェトキシ基、ベンジルオキシ基、コーフェニル
エトキシ基などが挙げられる。アリールオキシ基として
は、例えばフェノキシ基、≠−ｔ−ブチルフェノキシ基
、≠−クロロフェノキシ基などが挙げられる。Examples of the aryl group include a phenyl group, a goomethylphenyl group, a 3-methoxyphenyl group, and a ≠-chlorophenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group include methoxy group, butoxy group, comethoxyethoxy group, benzyloxy group, and cophenylethoxy group. Examples of the aryloxy group include phenoxy group, ≠-t-butylphenoxy group, and ≠-chlorophenoxy group.
アシルアミノ基としては例えばアセチルアミノ基、メタ
ンスルホニルアミノ基、ベンゾイルアミノ基、≠−メチ
ルベンゼンスルホニルアミノ基などが挙げられる。カル
バモイル基としては例えばカルバモイル基、Ｎ−メチル
カルバモイル基、Ｎ−エチルカルバモイル基、Ｎ−フェ
ニルカルバモイル基などが挙げられる。スルファモイル
基としては例えばスルファモイル基、Ｎ−メチルスルフ
ァモイル基、Ｎ−フェニルスルファモイル基などが挙ケ
られる。アシルオキシ基としては例えばアセチルオキシ
基、ピパロイルオキシ基、ベンゾイルオキシ基、ベンゼ
ンスルホニルオキシ基などが挙ケラれる。ウレイド基と
しては例えばメチルウレイド、エチルウレイド、フェニ
ルウレイドなどが挙げられる。Examples of the acylamino group include an acetylamino group, a methanesulfonylamino group, a benzoylamino group, and a ≠-methylbenzenesulfonylamino group. Examples of the carbamoyl group include carbamoyl group, N-methylcarbamoyl group, N-ethylcarbamoyl group, and N-phenylcarbamoyl group. Examples of the sulfamoyl group include a sulfamoyl group, an N-methylsulfamoyl group, and an N-phenylsulfamoyl group. Examples of the acyloxy group include an acetyloxy group, a piparoyloxy group, a benzoyloxy group, and a benzenesulfonyloxy group. Examples of the ureido group include methylureido, ethylureido, and phenylureido.
Ｚ２１７Ｃよって形成されるピロール環としては、例、
ｔばピロール、インドール、コーメチルインドール、よ
−メトキシインドール、よ−ヒドロキシインドール、Ｌ
−トリプトファンカルバゾール、３−カルボキシインド
ール、２．！−ジメチルピロールなどが挙げられる。イ
ミダゾール環としては例えば、イミダゾール、λ−メチ
ルイミダゾール、コーエチルイミダゾール、λ−ウンデ
シルイミダゾール、λ−フェニルイミダゾール、λ、４
Ｃ−ジメチルイミダゾール、コーエチルー≠−メチルイ
ミダゾール、Ｌ−ヒスチジン、≠、ｊ−ジフェニルイミ
タソール、コ、係、ｒ−トリフェニルイミダゾール、ベ
ンゾイミダゾール、コーメチルベンゾイミダゾール、λ
−メチルー！−クロロベンゾイミダゾール、コーメチル
ー！、６−ジクロロベンゾイミダゾール、コーメチルー
！−クロローＪ−シアノベンゾイミダゾール、コーメル
カブトベンゾイミダゾールなどが挙げられる。ピラゾー
ル環としては例えばピラゾール、３．ｊ−ジメチルピラ
ゾール、３．ｊ−ジフェニルピラゾール、μｍブロモ−
３，！−ジメチルピラゾール、３−メチルピラゾール、
インダゾールなどが挙げられる。トリアゾール環として
は／、！、４ｃｍトリアゾール、／、２，４ｃ−トリア
ゾール、コークロロー／、３．≠−トリアゾール、コ、
！−ジメチルー／、Ｊ、４ｔ−トリアゾール、３．！−
ジ７工二ルー／、２，４ｃｍ１リアゾール、ベンゾトリ
アゾールなどが挙げられる。テトラゾール環としては、
例えばテトラゾール、！−フェニルテトラゾールなどが
挙げられる。Examples of the pyrrole ring formed by Z217C include:
t-pyrrole, indole, co-methylindole, methoxyindole, hydroxyindole, L
-Tryptophan carbazole, 3-carboxindole, 2. ! -dimethylpyrrole and the like. Examples of the imidazole ring include imidazole, λ-methylimidazole, coethylimidazole, λ-undecylimidazole, λ-phenylimidazole, λ, 4
C-dimethylimidazole, coethyl-≠-methylimidazole, L-histidine, ≠, j-diphenylimitasol, co-, r-triphenylimidazole, benzimidazole, comethylbenzimidazole, λ
-Methyl! -Chlorobenzimidazole, Komethyl-! , 6-dichlorobenzimidazole, comethyl! -Chloro J-cyanobenzimidazole, Komelkabutobenzimidazole, and the like. Examples of the pyrazole ring include pyrazole, 3. j-dimethylpyrazole, 3. j-diphenylpyrazole, μm bromo-
3,! -dimethylpyrazole, 3-methylpyrazole,
Examples include indazole. As a triazole ring /,! , 4cm triazole/, 2,4c-triazole, cochrolow/, 3. ≠−triazole, co,
! -dimethyl-/, J, 4t-triazole, 3. ! −
Examples include di7-di-ru/, 2,4cm1 lyazole, and benzotriazole. As a tetrazole ring,
For example, tetrazole! -phenyltetrazole and the like.
ま７ｔｚ２で示される環には一量体となシうる置換基（
例えば−５−）を有していてもよい。The ring represented by 7tz2 has a substituent that can form a monomer (
For example, it may have -5-).
以下に本発明に用いられる化合物の具体例を示すが、本
発明の範囲はこれらのみに限られるものではない。Specific examples of compounds used in the present invention are shown below, but the scope of the present invention is not limited to these.
これらの化合物は例えば下記反応式（１）に従って容易
に合成することができる。These compounds can be easily synthesized, for example, according to the following reaction formula (1).
用いる塩基としては、ピリジン、トリエチルアミン、／
、ｒ−ジアザビシクロＣＪ−１４’１（１））−７−ク
ンデセンのような有機塩基、炭酸カリウム、炭酸水素ナ
トリウム、カリウムｔ−ブトキシド、水素化ナトリウム
、水酸化ナトリウムのような無機塩基のいずれでもよい
溶媒としては、ｎ−ヘキサンのような炭化水素、テトラ
ヒドロフラン、ｌ。The base used is pyridine, triethylamine, /
, r-diazabicycloCJ-14'1(1))-7-kundecene, or inorganic bases such as potassium carbonate, sodium bicarbonate, potassium t-butoxide, sodium hydride, sodium hydroxide. Good solvents include hydrocarbons such as n-hexane, tetrahydrofuran, l.
−一ジメトキシエタンのようなエーテル、Ｎ、Ｎ−ジメ
チルホルムアミド、Ｎ−メチルピロリド／のようなアミ
ド、ジメチルスルホキシド、スルホランのような含硫黄
化合物、アセトニトリルのようなニトリル、酢酸エチル
のようなエステルなどが用いられる。中でもアミド、含
硫黄化合物、ニトリルが好ましい。まｔ反応温度に−１
００Ｃないし／ｊ００ｃ、好ましくは２ｏ ０ｃないし
１０ｏ ’Ｃが望ましい。-Ethers such as monodimethoxyethane, amides such as N,N-dimethylformamide and N-methylpyrrolid, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitrites such as acetonitrile, esters such as ethyl acetate, etc. used. Among these, amides, sulfur-containing compounds, and nitriles are preferred. -1 to the reaction temperature
00C to /j00c, preferably 2o 0c to 10o'C.
以下に、代表的化合物の合成例を示す。Synthesis examples of representative compounds are shown below.
（合成例）
合成例１、化合物ｌの合成
４Ａ−７にオロニトロベンゼ７／、ＩＡ／？（１０ミリ
モル）、ビロール０．ｔ７ｆ（１０ミリモル）。(Synthesis Example) Synthesis Example 1, Synthesis of Compound 1 4A-7 contains oronitrobenze 7/, IA/? (10 mmol), virol 0. t7f (10 mmol).
炭酸カリウム／、Ｊｔｆ（１０ミリモル）にｊ１１１７
のＮ、Ｎ−ジメチルホルムアミドを加え、り□。Ｃで弘
時間加熱攪拌した。反応混合物を水に注ぎ、得られ“た
結晶”ｔＦ取し、水洗した。粗結晶をインプロパツール
で１回再結晶を行ない目的の化合物ｌを得九〇収量／
、２ｉｔ（収率４４！、４！％）融点ｉｒｅ 〜ｉｖｙ
’ｃ
Ａ Ｅ＋ＯＨ＝ ｊ ２ Ａ ｎ ｍ
ａｘ
元素分析値 ＣＨＮ
実測＋１！ ６１４．０！ １１．／７ ／４ｃ
、！９ ％計算値 ６３．ｒコ ≠、コｒ／≠、ｒタ
チ合成例コ、化合物乙の合成
合成例／のピロール金２−エチルイミダゾールに替えて
同様に行なつ念。収量ｔ、ｇ３ｔ（収率７ｊ、／チ）融
点ｌＡ／−／６２ °Ｃ元素分析１直 ＣＨＮ
実測１［ＡＯ，ＦｔＡ ｕ、９４ Ｉ９．１ｆｉＯ
＊計算値 ｔＯ，Ｉ２ ！、１０ ／Ｙ＃Ｉｔ
％合成例３、化合物／２の合成
合成例１のピロールｆｃ！、！−ジメチルピラゾールに
替えて同様に行なつ几。収量／、！／１（収率６り、６
％）融点１０２ °Ｃ
元素分析＠ＣＨＮ
実測［４０，７ｔ ｌＡ、り１ １Ｆ、２６ ％計
算ｆ直 ｔＯ，Ｉ２ ｊ、１０ ／り、ｊ４Ｃ％合
成例≠、化合物ｌりの合成
合成例／のピロールｆ２．ｊ−ジメチル−７゜３、≠−
トリアゾールに替えて同様に行なつ之。Potassium carbonate/, JTF (10 mmol) to J1117
Add N,N-dimethylformamide and remove. The mixture was heated and stirred at C for a long time. The reaction mixture was poured into water, and the resulting "crystals" were collected and washed with water. The crude crystals were recrystallized once using Improper Tool to obtain the target compound l with a yield of 90/
, 2it (Yield 44!, 4!%) Melting point ire ~ivy
'c A E+OH= j 2 A n max Elemental analysis value CHN Actual measurement +1! 614.0! 11. /7 /4c
,! 9% calculated value 63. rco≠, kor/≠, rtati Synthesis example ①, synthesis of compound ① Synthesis of compound ① The same procedure should be carried out in place of pyrrole gold 2-ethylimidazole. Yield t, g3t (yield 7j, /chi) Melting point lA/-/62 °C Elemental analysis 1st shift CHN Actual measurement 1 [AO, FtA u, 94 I9.1fiO
*Calculated value tO,I2! , 10 /Y#It
% Synthesis Example 3, Synthesis of Compound/2 Pyrrole fc of Synthesis Example 1! ,! - Proceed in the same manner by replacing dimethylpyrazole. yield/,! /1 (yield 6, 6
%) Melting point 102 °C Elemental analysis @ CHN Actual measurement [40,7t lA, 1 1F, 26% Calculation f direct tO, I2 j, 10 /li, j4C% Synthesis example ≠, Synthesis example of compound l / Pyrrole f2. j-dimethyl-7゜3, ≠-
Do the same thing instead of triazole.
収ｔ／、＋ｔｒ（収率７！、６％）
融点／、４〜／！１．．．”ＣλＥ＋ＯＩＩ＝＝２ｒｔ
ｎｍ ａ ｘ
元素分析［ＣＨＮ
実測値 ！−！、２７ １１−．６ｊ ２！ｒ、！ｒ
％計算［！ｊ、０≠ ≠、２λ コよ、＋、ｒ
％（発明の効果）
本発明の化合物を用いることにより、青色光の透過率が
高く大きな非線形光学効果を示す材料を提供することが
できる。青色光の透過率の向上は、アミノ基の窒素原子
が複素芳香環に組込まれることによるニトロ基とＯＣＴ
相互作用の低下になると考えられ、効率の向上は、λつ
の環の同一平面からのずれ（極端な場合は分子不斉の誘
起）による配列の効果と考えられる。Yield t/, +tr (yield 7!, 6%) Melting point/, 4~/! 1. ．． ．． ”CλE+OII==2rt
nm a x elemental analysis [CHN actual value! -! , 27 11-. 6j 2! r,! r
% calculation [! j, 0≠ ≠, 2λ Koyo, +, r
% (Effect of the Invention) By using the compound of the present invention, it is possible to provide a material that has a high blue light transmittance and exhibits a large nonlinear optical effect. The improvement in the transmittance of blue light is due to the incorporation of the nitrogen atom of the amino group into the heteroaromatic ring, which is due to the nitro group and OCT.
This is thought to result in a decrease in interaction, and the improvement in efficiency is thought to be due to the arrangement effect due to deviation of the two rings from the same plane (in extreme cases, induction of molecular asymmetry).
他の化合物も上記の合成方法に本じて容易に行なうこと
ができる。Other compounds can also be easily synthesized using the above method.
本発明の化合物は、例えば粉末の形、宿主格子（ポリマ
ー、包接化合物、固溶体、液晶）中の分子の包有物の形
、支持体上に沈積した薄層の形（ラングミーア・プロジ
ェット膜など）、単結晶の形、溶液の形等、種々の形で
非線形光学材料として用いることができる。The compounds of the invention may be present, for example, in the form of a powder, in the form of molecular inclusions in a host lattice (polymers, clathrates, solid solutions, liquid crystals), in the form of thin layers deposited on a support (Langmeer-Prodgett membranes). It can be used as a nonlinear optical material in various forms such as single crystal form, solution form, etc.).
また本発明の化合物をインダントの形でポリマー、ポリ
ジアセチレｙなどに結合させて用いるとともできる。The compound of the present invention can also be used in the form of an indant bonded to a polymer, polydiacetyrene, or the like.
これらの方法について詳しくは前述のり、Ｊ。These methods are described in detail in the above-mentioned book, J.
Ｗｉ １１ ｉ ａｍｓ編の著作などに記載されている
。It is described in the works edited by Wi 11 i ams.
（実施例） 次に、本発明を実施例に基づいて詳しく説明する。(Example) Next, the present invention will be explained in detail based on examples.
実施例１
第２高調波発生の測定をニー・ケー・クルッ（Ｓ、に、
Ｋｕｒｔｚ ）、 ティー・ｆイー ・ばＩＪ−（Ｔ
、Ｔ、Ｐｅｒｒｙ ）著、ジャーナル オブ アプライ
ド フィジックス（Ｊ、Ａｐｐｌ、Ｐｈｙｓ−）３２巻
３７りｒ頁（ｌりｔｒ年刊）中に記載されている方法
に準じて、本発明の化合物の粉末に対して行なつ念。Example 1 Measurement of second harmonic generation was performed using
Kurtz), T.F.I.B.IJ-(T.
Powder of the compound of the present invention was prepared according to the method described in J., T. Perry), Journal of Applied Physics (J, Appl, Phys-), Vol. 32, p. 37. I wish I could do it.
線源としてＮｄ：ＹＡＧレーザ−（ｊＯｍＷパルス）の
ｉ、ｏｔμμ線を１史用し、ガラスセル中に充填し次粉
末のサンプルに照射し、！３２ｎｍ（Ｄ緑色光の発生を
観測し次。結果を表／に示す。The i,otμμ rays of a Nd:YAG laser (jOmW pulse) were used as a radiation source, filled in a glass cell, and then irradiated onto a powder sample. The generation of green light was observed at 32 nm (D). The results are shown in Table 1.
＊尿素を／とし之ときの相対強度。*Relative strength of urea.
光電子増倍管により検出し友。Detected by photomultiplier tube.
実施例λ
伊色光の透過性を調べるため、下記の化合物の≠×７０
モル／ｌのエタノール溶液の波長に対する透過率を
測定し友。結果を図／に示した。Example λ In order to investigate the transmittance of Ichroic light, the following compound was used at ≠×70
Measure the transmittance of a mol/l ethanol solution at different wavelengths. The results are shown in Figure/.
ＭＮＡ ＰＮＰ
ＰＡＮ第１図から明らかなように本発明の化合物は背
色光の透過性において優れたものである。MNA PNP
As is clear from FIG. 1 of the PAN, the compound of the present invention is excellent in transmittance of back-colored light.
実施例１およびコから明らかなように本発明の化合物は
高い非線形光学率と、高い實色光透過性を示す。As is clear from Examples 1 and 2, the compounds of the present invention exhibit high nonlinear optical efficiency and high true color light transmittance.
第１図は、実施例２における各化合物のエタノール溶液
中における分光透過率を示した。
図中■〜■は、各々化合物／り、６．１２、／、ＰＮＰ
、ＭＮＡ、ＰＡＮ′１に示す。
なお、縦軸は、透過率（Ｔ９６）ｔ−１横軸は波長（ｎ
ｍ ）を表わす。
特許出願人 富士写真フィルム株式会社３００ ３５
０ ４００ ４５０ｎｒｎ手続補正書
昭和４／、年φ月２９日
特許庁長官 殿 １へ１、
事件の表示 昭和６７年特特訓ＪＪｒｒ≠号２、
発明の名称 非線形光学材料
３、補正をする者
事件との関係 特許出願人性 所 神奈
川県南足柄市中沼２１０番地゛電話（４０（ｉ） ２５
３７
４、補正の対象 明細書の「発明の詳細な説明の欄
５、補正の内容
明細書の「発明の詳細な説明」の項の記載を下記の通り
補正する。
／）第−頁コ行目の
「親規」を
「新規」
と補正する
２）第１３頁下から７行目の
「いずれでもよい」の後Ｋ
「。」
を挿入する
り＠／μ頁１７行目の
と補正する
り第７３頁！行目の
」
ｍａＪを
ｍａｘ 」
と補正する
ｊ）第１ｊ頁１３行目の
ｍａＪを
ｍａｘ Ｊ
と補正する
６）第７６頁３行目の
ｍａＪを
ｍａｘ Ｊ
と補正する
７）第１７頁λ行目の
「プロジェット」を
「プロジェット」
と補正する
ｒ）第１ｒ頁下から一行目の
「≠Ｘ１Ｏ−３Ｊを
「弘Ｘ１Ｏ−４Ｊ
と補正する
手続補正書
昭和６１年２月ｉ日
１、事件の表示 昭和６１年特特訓５ｚｒｒｐ
号・２０発明の名称 非線形光学材料３、補正を
する者
事件との関係 特許出願人件 所 譬Ｊ
、１．！腎南足柄市中沼２１０番地４、補正の対象
明細書の「発明の詳細な説明」の欄、「図面の簡単な説
明」
の欄
５、補正の内容
明細書の「発明の詳細な説明」の項の記載を下記の通り
補正する。
１）第１２頁と第１３頁の間に別紙を挿入する。
２）第１！頁１７行目の
「化合物ｌりの合成」を
「化合物λりの合成」
と補正する。
３）第１！頁ｉｔ行目の
「λ、ｊ−ジメチルー／、」を
ｒｔＨ−ｓ、ｓ−ジメチル−／、Ｊ
と補正する。
４）第１６頁／行目の
「３．グー」を
「コ９μｍ」
と補正する。
５）第ｉｔ頁表／の
「化合物欄のｌり」を
「２り」
と補正する。
６）第１り頁／行目の
「化合物／り」を
「化合物コタ」
と補正する。
明細書の「図面の簡単な説明」の項の記載を下記の通り
補正する。
７）第２０頁λ行目の
「化合物ｌり」を
「化合物λり」
と補正する。
別紙
Ｏ２
Ｏ２
昭和３２年３月り日
１、事件の表示 昭和４／年待願第に’Ｊｌｌｌ
ｆｉ号２、発明の名称 非線形光学材料
３、補正をする者
事件との関係 特許出願人４、補正の対象
明細書の「発明の詳細な説明」の欄
５、補正の内容
明細書の「発明の詳細な説明Ｊの項の記載を下記の通り
補正する。
第１コ頁の化合物２７の
」
と補正する。
手続補正書FIG. 1 shows the spectral transmittance of each compound in Example 2 in an ethanol solution. In the figure, ■ to ■ are the compounds /ri, 6.12, /, PNP, respectively.
, MNA, PAN'1. Note that the vertical axis represents the transmittance (T96) and the horizontal axis represents the wavelength (n
m ). Patent applicant Fuji Photo Film Co., Ltd. 300 35
0 400 450nrn Procedural Amendment 1939/, 29th φ month Dear Commissioner of the Patent Office, 1 to 1,
Display of incident 1986 special training JJrr≠No. 2,
Title of the invention: Nonlinear optical material 3, relationship with the person making the correction Case: Patent applicant: Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Telephone number: 40(i) 25
37 4. Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the contents of the amendment is amended as follows. /) Correct the "main regulations" on the 7th line of the -th page to "new" 2) Insert K "." after "Anything is fine" on the 7th line from the bottom of the 13th page @/μ page Correct the 17th line on page 73! Correct maJ on line 1j to max j) Correct maJ on page 1j, line 13 to max J 6) Correct maJ on page 76, line 3 to max J 7) Correct page 17, line λ Procedural amendment to amend "≠X1O-3J" in the first line from the bottom of page 1r to "Hiroshi Incident display 1985 special training 5zrrp
No. 20 Title of the invention Nonlinear optical material 3, Relationship to the amended person case Patent applicant Location Parable J
, 1. ! 210-4 Nakanuma, Renminami Ashigara City, subject to correction
The statements in the "Detailed Description of the Invention" column of the specification, the "Brief Description of Drawings" column 5, and the "Detailed Description of the Invention" section of the description of the contents of the amendment are amended as follows. 1) Insert a separate sheet between pages 12 and 13. 2) First! "Synthesis of compound 1" on page 17 line is corrected to "synthesis of compound λ". 3) First! "λ, j-dimethyl-/," in the it-th line of the page is corrected to rtH-s, s-dimethyl-/, J. 4) Correct "3. Goo" on the 16th page/line to "K9μm". 5) Correct "1 in the compound column" in the table on page it to "2". 6) Correct "Compound/ri" on the first page/line to "Compound Kota". The description in the "Brief Description of Drawings" section of the specification is amended as follows. 7) Correct "Compound 1" on page 20, line λ to "Compound 1". Attachment O2 O2 Date 1, March 1950, Display of the incident
fi No. 2, Title of the invention Nonlinear optical material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment Column 5 of "Detailed explanation of the invention" in the specification, "Invention of the invention" in the description of the contents of the amendment The description in section J of Detailed Description of ``Compound 27'' on page 1 is amended as follows. Procedural amendment
Claims (1)
付加物からなることを特徴とする非線形光学材料 一般式（ I ） ▲数式、化学式、表等があります▼ （式中、Ｚ＾１は少くとも１つのニトロ基を置換基とし
て有する５ないし６員芳香族環を形成するに必要な原子
群を表わす。Ｚ＾２は置換および縮環されていてもよい
、ピロール環、イミダゾール環、ピラゾール環、トリア
ゾール環、またはテトラゾール環を形成するに必要な原
子群を表わす。）[Claims] A nonlinear optical material characterized by comprising a compound represented by the following general formula (I) or an acid adduct thereof General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z^1 represents an atomic group necessary to form a 5- to 6-membered aromatic ring having at least one nitro group as a substituent; Z^2 is a pyrrole ring which may be substituted or fused; Represents the atomic group necessary to form an imidazole ring, pyrazole ring, triazole ring, or tetrazole ring.)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5388486A JPH0711646B2 (en) | 1986-03-12 | 1986-03-12 | Non-linear optical material |
| DE19873707835 DE3707835A1 (en) | 1986-03-11 | 1987-03-11 | NON-LINEAR OPTICAL MATERIAL |
| US07/263,977 US4982112A (en) | 1986-03-11 | 1988-10-26 | Nonlinear optical material |
| US07/598,514 US5115337A (en) | 1986-03-11 | 1990-10-16 | Nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5388486A JPH0711646B2 (en) | 1986-03-12 | 1986-03-12 | Non-linear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62210432A true JPS62210432A (en) | 1987-09-16 |
| JPH0711646B2 JPH0711646B2 (en) | 1995-02-08 |
Family
ID=12955164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5388486A Expired - Fee Related JPH0711646B2 (en) | 1986-03-11 | 1986-03-12 | Non-linear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0711646B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0229A (en) * | 1987-09-14 | 1990-01-05 | Fuji Photo Film Co Ltd | Optical wavelength conversion method |
| JPH0277181A (en) * | 1988-09-13 | 1990-03-16 | Fuji Photo Film Co Ltd | Laser diode pomping solid laser |
| JPH039585A (en) * | 1989-06-07 | 1991-01-17 | Fuji Photo Film Co Ltd | Laser diode pumping solid-state laser |
| US5029976A (en) * | 1988-10-19 | 1991-07-09 | Fuji Photo Film Co., Ltd. | Optical wavelength converter device and optical wavelength converter module |
| US5080462A (en) * | 1989-11-02 | 1992-01-14 | Fuji Photo Film Co., Ltd. | Optical wavelength converter device and optical wavelength converter system |
| US5187714A (en) * | 1990-10-19 | 1993-02-16 | Fuji Photo Film Co., Ltd. | Laser-diode-pumped solid-state laser |
| US5286872A (en) * | 1991-05-21 | 1994-02-15 | Fuji Film Co., Ltd. | Deuterated pyrazole compound |
| US5341393A (en) * | 1990-05-10 | 1994-08-23 | Fuji Photo Film Co., Ltd. | Laser-diode-pumped solid-state laser |
-
1986
- 1986-03-12 JP JP5388486A patent/JPH0711646B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0229A (en) * | 1987-09-14 | 1990-01-05 | Fuji Photo Film Co Ltd | Optical wavelength conversion method |
| JPH0277181A (en) * | 1988-09-13 | 1990-03-16 | Fuji Photo Film Co Ltd | Laser diode pomping solid laser |
| US5029976A (en) * | 1988-10-19 | 1991-07-09 | Fuji Photo Film Co., Ltd. | Optical wavelength converter device and optical wavelength converter module |
| JPH039585A (en) * | 1989-06-07 | 1991-01-17 | Fuji Photo Film Co Ltd | Laser diode pumping solid-state laser |
| US5080462A (en) * | 1989-11-02 | 1992-01-14 | Fuji Photo Film Co., Ltd. | Optical wavelength converter device and optical wavelength converter system |
| US5341393A (en) * | 1990-05-10 | 1994-08-23 | Fuji Photo Film Co., Ltd. | Laser-diode-pumped solid-state laser |
| US5187714A (en) * | 1990-10-19 | 1993-02-16 | Fuji Photo Film Co., Ltd. | Laser-diode-pumped solid-state laser |
| US5286872A (en) * | 1991-05-21 | 1994-02-15 | Fuji Film Co., Ltd. | Deuterated pyrazole compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0711646B2 (en) | 1995-02-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |