JPH02264788A - Nickel complex - Google Patents
Nickel complexInfo
- Publication number
- JPH02264788A JPH02264788A JP1087640A JP8764089A JPH02264788A JP H02264788 A JPH02264788 A JP H02264788A JP 1087640 A JP1087640 A JP 1087640A JP 8764089 A JP8764089 A JP 8764089A JP H02264788 A JPH02264788 A JP H02264788A
- Authority
- JP
- Japan
- Prior art keywords
- complex
- nickel
- methoxy
- methoxyethoxy
- added
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 26
- 229910052759 nickel Inorganic materials 0.000 title abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical group 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000010992 reflux Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 2
- ZXSYCIPIPAEKCC-UHFFFAOYSA-N 3-[2-(2-chlorophenyl)ethenyl]-1-methoxy-6-(2-methoxyethoxy)cyclohexa-3,5-diene-1,2-dithiol Chemical compound COCCOC1=CC=C(C(C1(OC)S)S)C=CC2=CC=CC=C2Cl ZXSYCIPIPAEKCC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000004040 coloring Methods 0.000 abstract 2
- BWSFAZMZEZVRMS-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-hydroxy-1-[3-methoxy-4-(2-methoxyethoxy)phenyl]ethanone Chemical compound C1=C(OC)C(OCCOC)=CC=C1C(=O)C(O)C1=CC=CC=C1Cl BWSFAZMZEZVRMS-UHFFFAOYSA-N 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- -1 amyloxy group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OWTXHNANQTWFLX-UHFFFAOYSA-N 1-(2-chlorophenyl)-2-hydroxy-2-phenylethanone Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1Cl OWTXHNANQTWFLX-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-O 1H-indol-1-ium Chemical compound C1=CC=C2[NH2+]C=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-O 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XQNIYBBHBZAQEC-UHFFFAOYSA-N diphosphorus trisulphide Chemical compound S=PSP=S XQNIYBBHBZAQEC-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012015 optical character recognition Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Filters (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
〈産業上の利用分野〉
近赤外域に吸収をもつ色素はコンピューターやファクシ
ミリなどに入力装置として使用される光学式文字読み取
り装置、赤外線カットフィルター、電子写真方式プリン
ターの感光部あるいは半導体レーザーによる書き込みと
再生が可能な光デイスク用被膜等として利用されている
（早用茂、エレクトロニクス、２８，４７５ （１９８
３）。本発明はこれらの分野に利用することのできる特
定の構造を有するニッケル錯体に関する発明である。
〈従来の技術〉
有機化合物とくにポリオレフィン化合物を光に対して安
定化さすために、非常に多（のジチオカルボニル金属錯
体が報告されている。例えばジャーナル・オブ・ザ修ア
メリカン・ケミカル・ソサイエティ、８７巻、１４８３
−１４８９ （１９６５）、ドイツ特許１，２１１，６
２９、同２，１４４，８０１、アメリカ特許３，８９４
，０６９．特公昭５７−３０１０１．同５８−１０５９
６０、特開昭６１−１３７３６等である。これらの化合
物はポリオレフィン化合物の光による分解を抑制し、か
つ活性酸素、フリーラジカルのレセプターとして有効な
物であるが次の理由でさらに改良が強く望まれている。
即ち電子写真の感光部あるいは光ディスクに用いる際、
均一な薄膜を形成する必要がある。薄膜形成には湿式及
び乾式法があるが、材料を溶剤にとかしてローラーコー
ティング法、スピンコーティング法等により膜を形成す
る湿式法が量産性に優れ、安価であり実用的である。
有機化合物は基本的にこの湿式法が採用できるため、近
年非常に注目され、精力的にその研究開発が進められて
いる。しかし赤外領域に吸収を有する材料は一般に溶解
性に劣るものが多く、実用的な湿式法を採用するために
は材料の溶解性が大きな問題となっている。
〈発明が解決しようとする問題点〉
現在、ジチオカルボニル金属錯体を光デイスク用記録媒
体として、あるいは他の色素類とともに用いて活性酸素
のクエンチャ−として利用するために、一般式（３）ま
たは（４）で表されるニッケル錯体が実用材料として提
案されている。ところがこれらの錯体はいまなお溶解性
に問題があり、薄膜上での結晶化によるＳ／Ｎ比の低下
、使用できる溶剤の種類の限定、およびこれに伴い基板
の材質が限定される等、品質上、製造上あるいは経済上
なお不満足なものであり、これらの条件設定に苦慮しな
がら使用しているのが実状である。
式（３）（公知錯体ｌ）
式（４）（公知錯体２）
く問題を解決する為の手段〉
本発明者等は鋭意研究の結果、特定の構造を有する新規
なニッケル錯体を見出し、本発明を完成したものであり
、本発明は一般式（１）または（２）で表されるジチオ
カルボニルニッケル錯体に関するものである。
一般式（１）
または一般式（２）
上式においてＲ，は水素、低級アルキル基を表し、鳥は
水素、またはフッ素、塩素、臭素などのハロゲンを表す
。Ｘは水素、またはメトキシ基、エトキシ基、イソブト
キシ基、アミロキシ基などのアルコキシ基または
−０→ＣＨ，？ＯＲ，を表す。またｍは１〜３の整数、
ｎは１〜４の整数を表す。Ａは第４級アンモニウム塩ま
たはシアニン色素のカチオン部を表す。
本発明になる一般式（１）記載のニッケル錯体はたとえ
ばＪ、Ａ、Ｃ，Ｓ、８７．１４８３ （１９６５）記載
の方法に基づき、また一般式（２）の錯体は一般式（１
）の錯体を用いて、たとえば夏ｎｏｒｇ、 Ｃｈｅ＋ｍ
、 ｇ 、 １２２７（１９６３）記載の方法に基づい
て合成することができる。以下に実施例をあげて本発明
を更に詳細に説明する。ただし、本発明はこれらの実施
例に限定されるものではない。
実施例１
ビス（３−メトキシ−４−メトキシエトキシ−２′−ク
ロロスチルベンジチオレート）ニッケル（以下、錯体ｌ
と称す）の製法
３−メトキシ−４−（２−メトキシエトキシ）−２′−
クロロベンゾイン３５ｇと三硫化リン４８ｇをジオキサ
ン４００ ｍ ｌ中で８時間還流撹拌し、それから反応
液を室温まで冷却し、これに塩化ニッケル２８ｇの水溶
液３００ ｍ ｌを加え、３時間還流撹拌した。冷却さ
れた反応液にクロロホルムを加えて抽出し、クロロホル
ム層を水洗、乾燥後濃縮した。
得られた残渣をシリカゲルカラムクロマトグラフィーに
より精製し、メタノールより再結晶することにより、目
的錯体ｌを得た。このものの吸収極大波長（λｍ ａ
ｘ ）は塩化メチレン中で８８３ ｎ ｍ 、分子吸光
係数εは２．７２ ｘ １０’、融点（ｍ、ｐ、）は１
４３〜１４５℃であつた。
実施例２
テトラ−ｎ−ブチルアンモニウム ビス<Industrial Application Fields> Dyes that absorb in the near-infrared region are used in optical character readers used as input devices in computers and facsimiles, infrared cut filters, photosensitive parts of electrophotographic printers, and writing with semiconductor lasers. It is used as a coating for reproducible optical discs (Shigeru Hayayo, Electronics, 28,475 (198
3). The present invention relates to a nickel complex having a specific structure that can be used in these fields. <Prior art> A large number of dithiocarbonyl metal complexes have been reported for stabilizing organic compounds, especially polyolefin compounds, against light. For example, Journal of the American Chemical Society, 87 Volume, 1483
-1489 (1965), German Patent No. 1,211,6
29, 2,144,801, U.S. Patent 3,894
,069. Tokuko Sho 57-30101. 58-1059
60, JP-A No. 61-13736, etc. Although these compounds suppress the decomposition of polyolefin compounds by light and are effective as receptors for active oxygen and free radicals, further improvements are strongly desired for the following reasons. That is, when used in electrophotographic photosensitive parts or optical discs,
It is necessary to form a uniform thin film. There are wet and dry methods for forming thin films, and the wet method, in which a material is dissolved in a solvent and a film is formed by roller coating, spin coating, etc., is superior in mass production, inexpensive, and practical. Since this wet method can basically be applied to organic compounds, it has attracted a lot of attention in recent years, and its research and development is being actively pursued. However, many materials that absorb in the infrared region generally have poor solubility, and the solubility of the material is a major problem in adopting a practical wet method. <Problems to be Solved by the Invention> Currently, in order to utilize dithiocarbonyl metal complexes as recording media for optical discs or as quenchers for active oxygen when used with other dyes, the general formula (3) or ( A nickel complex represented by 4) has been proposed as a practical material. However, these complexes still have problems with their solubility, and quality issues such as a decrease in the S/N ratio due to crystallization on thin films, limitations on the types of solvents that can be used, and limitations on substrate materials are associated with this. However, it is still unsatisfactory in terms of manufacturing and economics, and the reality is that it is used with great difficulty in setting these conditions. Formula (3) (Known Complex 1) Formula (4) (Known Complex 2) Means for Solving the Problem> As a result of intensive research, the present inventors discovered a new nickel complex having a specific structure, and the present inventors The invention has been completed, and the present invention relates to a dithiocarbonyl nickel complex represented by general formula (1) or (2). General Formula (1) or General Formula (2) In the above formula, R represents hydrogen or a lower alkyl group, and ``bird'' represents hydrogen or a halogen such as fluorine, chlorine, or bromine. X is hydrogen, or an alkoxy group such as a methoxy group, ethoxy group, isobutoxy group, or amyloxy group, or -0→CH, ? represents OR. Also, m is an integer from 1 to 3,
n represents an integer of 1 to 4. A represents a quaternary ammonium salt or a cation moiety of a cyanine dye. The nickel complex of the general formula (1) according to the present invention is based on the method described in J, A, C, S, 87.1483 (1965), and the complex of the general formula (2) is prepared based on the method described in the general formula (1)
), for example, summer norg, Che+m
, G, 1227 (1963). The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to these examples. Example 1 Bis(3-methoxy-4-methoxyethoxy-2'-chlorostilbenedithiolate)nickel (hereinafter referred to as complex l
3-Methoxy-4-(2-methoxyethoxy)-2'-
35 g of chlorobenzoin and 48 g of phosphorus trisulfide were stirred under reflux in 400 ml of dioxane for 8 hours, then the reaction solution was cooled to room temperature, 300 ml of an aqueous solution of 28 g of nickel chloride was added thereto, and the mixture was stirred under reflux for 3 hours. Chloroform was added to the cooled reaction solution for extraction, and the chloroform layer was washed with water, dried, and concentrated. The obtained residue was purified by silica gel column chromatography and recrystallized from methanol to obtain the target complex 1. Maximum absorption wavelength of this substance (λm a
x) is 883 nm in methylene chloride, the molecular extinction coefficient ε is 2.72 x 10', and the melting point (m, p,) is 1
The temperature was 43-145°C. Example 2 Tetra-n-butylammonium bis
【（３−メトキ
シ−４−（２−メトキシエトキシ）−２′ −クロロ
スチルベンジチオレートへ】ニッケレート（錯体２）の
製法
錯体ｌのｔｇを塩化メチレン１２０ ｍ ｌに溶した液
にパラフェニレンジアミン ０．４ｇを加え、室温で１
５分撹拌した後、テトラ−ｎ−ブチルアンモニウムクロ
ライド１．６ｇを加え、更に４０分間撹拌した。
その後溶媒を留去し粗結晶を得、これを再結晶して目的
錯体２を得た。このもののλｍ ａ ｘは塩化メチレン
中で９３４ｎｍ、εは１．３７Ｘ１０’、ｍ 、 ｐ
、は６９〜７１’Ｃであった。
実施例３
１．３．３−トリメチル−２−（７−（１，３，３−ト
リメチル−２−インドリニリデン）−１，３，５−へブ
タトリエニル〕−３Ｈ−インドリウム ビス〔３−メト
キシ−４−（２−メトキシエトキシ）−２′−クロロス
チルベンジチオレート〕ニツケレー１．３．３−トリメ
チル−２−（７−（１，３，３−トリメチル−２−イン
ドリニリデン）−Ｌ３．５−へブタトリエニル〕−３Ｈ
−インドリウムヨーシト０．３ｇをアセトン１ 、５
ｍ ｌに加熱完溶させ、これに錯体２の０．４３ｇをア
セトン５ｍｌに加熱完溶した溶液を加えて、１０分間還
流した後濾過し、濾液にメタノール２０ｍ１を加えて冷
却し、析出した結晶を濾取する。得られた結晶をメタノ
ールで煮沸、冷却した後濾取し、目的錯体３を得た。こ
のものの塩化メチレン中のλｍ ａ ｘは７５６ 、９
２５ ｎ ｍ 、εはそれぞれ２．８２ ｘ １０’、
！、６２ ｘ １０’、ｍ 、 ｐ 、は１６８〜１
６９℃であった。
実施例４
実施例１と同様にして以下の代表的錯体を得た。
錯体４
錯体５
錯体６
錯体７
錯体８
く作用〉
本発明になるニッケル錯体は塩化メチレン中で約７５０
ｎｍから約１２００ｎｍにわたる赤外域に吸収を有する
色素群であり、各色素は約３００ｎｍにおよぶ広い吸収
帯を有している。
たとえば錯体ｌではλｍ ａ ｘは前記の如（，８８３
ｎｍであり、短波長側吸収端は約７５０ｎｍにあり、長
波長側は約１１０５０ｎにある。またε値は約１万から
３万の範囲にある。
第１表は本発明錯体と公知錯体の溶解性についての比較
例を示すもので、番号ｌと２の比較から、本発明になる
錯体ｌは公知錯体ｌに比べて、ｌ、２ジクロルエタン（
ＤＣＥ）で約３倍、メチルエチルケトン（ＭＥＫ）で約
１６倍、エチレングリコールモノエチルエーテル（ＥＧ
ＭＥ）で約７８倍、エタノールで約６９倍という優れた
溶解性を示す。また番号３と４の比較から、本発明にな
る錯体２はＤＣＥやＭＥＫでは公知錯体２とほぼ同じ溶
解性を示すが、ＥＧＭＥでは、約９倍、ＥｔＯＨでは約
１４倍の溶解性を示す。
本発明の他の錯体もほぼ同様の改良された溶解性を示す
。
第１表
なお、溶解度は各サンプルを含む溶媒を３時間超音波発
生器中に保持した後過剰のサンプル結晶を濾別し、濾液
の一定量より比色定量法により求められた。
第１図は本発明になるニッケル錯体のシアニン色素に対
するクエンチング特性を示す図であり、各サンプルの塩
化メチレン溶液に、島津製キセノンフェードテスター′
で１２００Ｗのキセノン光を照射し、各時間における吸
光度を測定し残存率を求め図にしたものである。図より
本発明になる錯体Ｉはシアニン色素（ＮＫ１２５）の耐
光性を大巾に向上させる効果があり、この効果は公知錯
体ｌよりも大きいことが判る。なおＮＫ１２５は次の構
造を有する。
Ｋ１２５
リカーボネート樹脂系基板にも使用が可能となりた。
本発明の他の錯体も同様の効果を示す。
〈発明の効果〉
本発明になるニッケル錯体は赤外域に吸収を有し、赤外
線吸収色素として有用である。またこれらの錯体はケト
ン系やハロゲン系溶媒だけでなく、エチレングリコール
モノエチルエーテルやエタノールなどのアルコール系溶
媒に対する溶解度の向上により、湿式法例えばスピンコ
ード法により薄膜を形成する際に要求される溶解性を備
えており、シアニン色素等の安定剤として光デイスク記
録媒体として有用である。アルコール系溶媒に対する溶
解性の向上により、アクリル樹脂系のみならずボ[To (3-methoxy-4-(2-methoxyethoxy)-2'-chlorostilbenedithiolate]) Process for producing nickelate (complex 2) Add paraphenylene diamine to a solution of tg of complex l in 120 ml of methylene chloride. Add 0.4g and 1 at room temperature.
After stirring for 5 minutes, 1.6 g of tetra-n-butylammonium chloride was added, and the mixture was further stirred for 40 minutes. Thereafter, the solvent was distilled off to obtain crude crystals, which were recrystallized to obtain the target complex 2. The λmax of this product is 934 nm in methylene chloride, and the ε is 1.37X10', m, p
, was 69-71'C. Example 3 1.3.3-Trimethyl-2-(7-(1,3,3-trimethyl-2-indolinylidene)-1,3,5-hebutatrienyl]-3H-indolium bis[3- Methoxy-4-(2-methoxyethoxy)-2'-chlorostilbenedithiolate]Nitsukele 1.3.3-Trimethyl-2-(7-(1,3,3-trimethyl-2-indolinylidene)-L3 .5-hebutatrienyl]-3H
- 0.3 g of indolium iosite and 1,5 g of acetone
A solution of 0.43 g of Complex 2 dissolved in 5 ml of acetone by heating was added thereto, and after refluxing for 10 minutes, it was filtered. 20 ml of methanol was added to the filtrate and cooled, and the precipitated crystals were dissolved. filtrate. The obtained crystals were boiled with methanol, cooled and collected by filtration to obtain the target complex 3. The λmax of this product in methylene chloride is 756, 9
25 nm, ε is 2.82 x 10', respectively.
! , 62 x 10', m, p, is 168~1
The temperature was 69°C. Example 4 The following representative complex was obtained in the same manner as in Example 1. Complex 4 Complex 5 Complex 6 Complex 7 Complex 8 Action> The nickel complex of the present invention has a nickel complex of about 750% in methylene chloride.
It is a group of dyes that have absorption in the infrared region ranging from nm to about 1200 nm, and each dye has a wide absorption band of about 300 nm. For example, in complex l, λm a x is as described above (,883
The absorption edge on the short wavelength side is at about 750 nm, and the absorption edge on the long wavelength side is at about 11050 nm. Moreover, the ε value is in the range of approximately 10,000 to 30,000. Table 1 shows comparative examples regarding the solubility of the complex of the present invention and the known complex. From the comparison of numbers 1 and 2, the complex 1 of the present invention has a higher solubility than the known complex 1 in 1,2 dichloroethane (
DCE), about 3 times, methyl ethyl ketone (MEK), about 16 times, ethylene glycol monoethyl ether (EG
It shows excellent solubility of about 78 times in ME) and about 69 times in ethanol. Further, from a comparison of Nos. 3 and 4, Complex 2 of the present invention exhibits almost the same solubility as the known Complex 2 in DCE and MEK, but exhibits about 9 times the solubility in EGME and about 14 times in EtOH. Other complexes of the invention exhibit much the same improved solubility. Table 1 Note that the solubility was determined by retaining the solvent containing each sample in an ultrasonic generator for 3 hours, filtering off excess sample crystals, and using a certain amount of the filtrate by a colorimetric method. Figure 1 is a diagram showing the quenching properties of the nickel complex of the present invention against cyanine dye.
The sample was irradiated with 1200W xenon light, the absorbance at each time was measured, and the residual rate was determined and plotted. From the figure, it can be seen that Complex I of the present invention has the effect of greatly improving the light resistance of cyanine dye (NK125), and this effect is greater than that of the known Complex I. Note that NK125 has the following structure. It is now possible to use K125 recarbonate resin substrates. Other complexes of the invention exhibit similar effects. <Effects of the Invention> The nickel complex of the present invention has absorption in the infrared region and is useful as an infrared absorbing dye. In addition, these complexes have improved solubility not only in ketone and halogenated solvents but also in alcoholic solvents such as ethylene glycol monoethyl ether and ethanol. It is useful as a stabilizer for cyanine dyes, etc. in optical disk recording media. Due to improved solubility in alcohol solvents, it can be used not only for acrylic resins but also for bottles.
第１図は本発明になるニッケル錯体のシアニン色素の耐
光性に及ぼす効果を示す図であり、縦軸は色素の残存率
（％）を、横軸は照射時間（ｈｒ）を表す。上はシアニ
ン色素ＮＫ１２５ （５ｍｇ）、芝はＮＫ１２５（５ｍ
ｇ）に錯体１ （２，５ｍｇ）を併用したもの、３はＮ
Ｋ −１２５（５ｍｇ）に公知錯体１ （２、５ｍ ｇ
）をキ
併用したものをそれぞれ、塩化メ嘱しンｌｏｍｊ＋の溶
液とし測定した。FIG. 1 is a diagram showing the effect of the nickel complex of the present invention on the light resistance of a cyanine dye, where the vertical axis represents the residual rate (%) of the dye and the horizontal axis represents the irradiation time (hr). The top is cyanine dye NK125 (5mg), the grass is NK125 (5m
g) in combination with Complex 1 (2.5 mg), 3 is N
Known complex 1 (2.5 mg) was added to K-125 (5 mg).
) was used in combination with each other as a solution of methane chloride lomj+ and was measured.
Claims (1)
素またはハロゲン、Ｘは水素、アルコキシ基または▲数
式、化学式、表等があります▼を表し、ｍは１〜３の整
数、ｎは１〜４の整数、Ａは第４級アンモニウム塩また
はシアニン色素のカチオン部を表す。）で表されるニッ
ケル錯体。[Claims] General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is hydrogen or a lower alkyl group, R_2 is Hydrogen or halogen; (represents the cation moiety of ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087640A JPH0745509B2 (en) | 1989-04-05 | 1989-04-05 | Nickel complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087640A JPH0745509B2 (en) | 1989-04-05 | 1989-04-05 | Nickel complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02264788A true JPH02264788A (en) | 1990-10-29 |
| JPH0745509B2 JPH0745509B2 (en) | 1995-05-17 |
Family
ID=13920583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087640A Expired - Lifetime JPH0745509B2 (en) | 1989-04-05 | 1989-04-05 | Nickel complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745509B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999010354A1 (en) * | 1997-08-26 | 1999-03-04 | Daihachi Chemical Industry Co., Ltd. | Phosphoric ester compounds and process for producing the same, copper phosphoric ester compounds and process for producing the same, near infrared absorber, and near infrared absorbent acrylic resin composition |
| EP1002832A1 (en) * | 1998-11-17 | 2000-05-24 | Nisshinbo Industries, Inc. | Near infrared absorption composition |
| US6117370A (en) * | 1998-11-11 | 2000-09-12 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| JP2000328039A (en) * | 1999-05-19 | 2000-11-28 | Hayashibara Biochem Lab Inc | Light absorber |
| JP2002350632A (en) * | 2001-05-30 | 2002-12-04 | Asahi Denka Kogyo Kk | Optical filter |
| WO2011068379A3 (en) * | 2009-12-03 | 2011-11-03 | (주) 경인양행 | Highly soluble and highly durable near-infrared absorbing compound and a near-infrared absorbing material comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6461492A (en) * | 1987-08-28 | 1989-03-08 | Midori Kagaku Co Ltd | Bis(dithiobenzyl) complex compound |
-
1989
- 1989-04-05 JP JP1087640A patent/JPH0745509B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6461492A (en) * | 1987-08-28 | 1989-03-08 | Midori Kagaku Co Ltd | Bis(dithiobenzyl) complex compound |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999010354A1 (en) * | 1997-08-26 | 1999-03-04 | Daihachi Chemical Industry Co., Ltd. | Phosphoric ester compounds and process for producing the same, copper phosphoric ester compounds and process for producing the same, near infrared absorber, and near infrared absorbent acrylic resin composition |
| US6410613B1 (en) | 1997-08-26 | 2002-06-25 | Kureha Kagaku Kogyo Kabushiki Kaisha | Phosphate compound and preparation process thereof, phosphate copper compound and preparation process thereof, near infrared ray absorber, and near infrared ray-absorbing acrylic resin composition |
| US6117370A (en) * | 1998-11-11 | 2000-09-12 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| EP1002832A1 (en) * | 1998-11-17 | 2000-05-24 | Nisshinbo Industries, Inc. | Near infrared absorption composition |
| KR20000035490A (en) * | 1998-11-17 | 2000-06-26 | 모치즈키 아키히로 | Near infrared absorption composition |
| US6217796B1 (en) * | 1998-11-17 | 2001-04-17 | Nisshinbo Industries, Inc. | Near infrared absorption composition |
| JP2000328039A (en) * | 1999-05-19 | 2000-11-28 | Hayashibara Biochem Lab Inc | Light absorber |
| JP2002350632A (en) * | 2001-05-30 | 2002-12-04 | Asahi Denka Kogyo Kk | Optical filter |
| JP4596682B2 (en) * | 2001-05-30 | 2010-12-08 | 株式会社Ａｄｅｋａ | Optical filter |
| WO2011068379A3 (en) * | 2009-12-03 | 2011-11-03 | (주) 경인양행 | Highly soluble and highly durable near-infrared absorbing compound and a near-infrared absorbing material comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745509B2 (en) | 1995-05-17 |
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