JPH0745509B2 - Nickel complex - Google Patents
Nickel complexInfo
- Publication number
- JPH0745509B2 JPH0745509B2 JP1087640A JP8764089A JPH0745509B2 JP H0745509 B2 JPH0745509 B2 JP H0745509B2 JP 1087640 A JP1087640 A JP 1087640A JP 8764089 A JP8764089 A JP 8764089A JP H0745509 B2 JPH0745509 B2 JP H0745509B2
- Authority
- JP
- Japan
- Prior art keywords
- complex
- present
- solubility
- nickel complex
- general formula
- 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.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052759 nickel Inorganic materials 0.000 title claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- -1 tetraalkylammonium cation Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000975 dye Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- 239000000460 chlorine Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate 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
- 238000010992 reflux Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JKXWXYURKUEZHV-UHFFFAOYSA-M (2z)-1,3,3-trimethyl-2-[(2e)-7-(1,3,3-trimethylindol-1-ium-2-yl)hepta-2,4,6-trienylidene]indole;iodide Chemical compound [I-].CC1(C)C2=CC=CC=C2N(C)C1=CC=CC=CC=CC1=[N+](C)C2=CC=CC=C2C1(C)C JKXWXYURKUEZHV-UHFFFAOYSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 239000007864 aqueous solution Substances 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
- 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
- 150000004696 coordination complex Chemical class 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
- 230000007423 decrease Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000000605 extraction Methods 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
- 230000001678 irradiating effect Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010791 quenching 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
- 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
- 239000000126 substance Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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)
Description
【発明の詳細な説明】 〈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
再生が可能な光ディスク用被膜等として利用されている
（早川茂，エレクトロニクス，28,475（1983）。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。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> Dyes having absorption in the near infrared region are optical character reading devices, infrared cut filters, and photosensitizers for electrophotographic printers used as input devices in computers and facsimiles. part or reproduction and writing by the semiconductor laser is utilized as an optical disc for coating such possible (Hayakawa, Shigeru, electronics, 28, 475 (1983). the present invention has a specific structure that can be utilized in these areas The invention relates to a nickel complex.
〈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、非常に多く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・ア
メリカン・ケミカル・ソサイェテイ、87巻、1483−1489
（1965）、ドイツ特許1,211,629、同2,144,801、アメリ
カ特許3,894,069、特公昭57−30101、同58−105960、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。<Prior Art> A large number of dithiocarbonyl metal complexes have been reported for stabilizing organic compounds, particularly polyolefin compounds against light. For example, Journal of the American Chemical Society, 87, 1483-1489.
(1965), German Patents 1,211,629, 2,144,801, US Patent 3,894,069, Japanese Patent Publications 57-30101, 58-105960, and JP 61-13736. These compounds suppress the decomposition of polyolefin compounds by light and are effective as receptors for active oxygen and free radicals, but further improvement is strongly desired for the following reasons. That is, it is necessary to form a uniform thin film when it is used for the photosensitive portion of electrophotography or an optical disc. There are wet and dry methods for forming a thin film, but a wet method of forming a film by dissolving a material in a solvent by a roller coating method, a spin coating method or the like is excellent in mass productivity, inexpensive, and practical. Since the wet method can be basically adopted for organic compounds, much attention has been paid in recent years, and research and development have been vigorously pursued. However, many materials that have absorption in the infrared region generally have poor solubility, and the solubility of the material is a major problem in adopting a practical wet method.
〈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ィスク用記録媒
体として、あるいは他の色素類とともに用いて活性酸素
のクエンチャー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。<Problems to be Solved by the Invention> Currently, in order to use a dithiocarbonyl metal complex as a recording medium for an optical disk or as a quencher for active oxygen by using it together with other dyes, a compound represented by the general formula (3) or (4) ) Has been proposed as a practical material. However, these complexes still have solubility problems, and the S / N ratio decreases due to crystallization on the thin film.
It is still unsatisfactory in terms of quality, manufacturing, and economics, such as limitations on the types of solvents that can be used and the materials for the substrates that accompany it. It is the actual situation.
〈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。 <Means for Solving the Problem> As a result of earnest research, the present inventors have found a novel nickel complex having a specific structure, and completed the present invention. The present invention has the general formula (1) or ( The present invention relates to a dithiocarbonyl nickel complex represented by 2).
上式においてR1は水素、低級アルキル基を表し、R2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 −ＯCH2 nOR1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。 In the above formula, R 1 represents hydrogen or a lower alkyl group, and R 2 represents hydrogen or halogen such as fluorine, chlorine or bromine.
X represents hydrogen, an alkoxy group such as a methoxy group, an ethoxy group, an isobutoxy group, an amyloxy group, or —OCH 2 n OR 1 . Further, m represents an integer of 1 to 3 and n represents an integer of 1 to 4. A represents a quaternary ammonium salt or a cation portion of a cyanine dye.
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Inorg,Chem.２,1227（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。The nickel complex represented by the general formula (1) according to the present invention is based on, for example, the method described in J, A, C, S, 87 , 1483 (1965), and the complex represented by the general formula (2) is represented by the general formula (1). The complex can be used to synthesize, for example, based on the method described in Inorg, Chem. 2 , 1227 (1963). Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
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１
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と五流化リン48gをジオキサン400m
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300ml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１を得た。このものの吸収極大波長（λma
x）は塩化メチレン中で338nm、分子吸光係数εは2.72×
104、融点（m.p.）は143〜145℃であった。Example 1 Bis (3-methoxy-4-methoxyethoxy-2'-chlorostilbenedithiolate) nickel (hereinafter referred to as complex 1
Referred to as “)” 3-methoxy-4- (2-methoxyethoxy) -2′-
Chlorobenzoin 35g and phosphorus pentachloride 48g in dioxane 400m
The mixture was stirred under reflux for 8 hours in 1L, then the reaction solution was cooled to room temperature, and 300 mL of an aqueous solution containing 28 g of nickel chloride was added thereto.
The mixture was stirred under reflux for hours. Chloroform was added to the cooled reaction solution for extraction, 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. Absorption maximum wavelength (λma
x) is 338 nm in methylene chloride, molecular extinction coefficient ε is 2.72 ×
10 4 , melting point (mp) was 143-145 ° C.
実施例２ テトラ−ｎ−ブチルアンモニウム 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〕ニッケレート（錯体２）の製法 錯体１の1gを塩化メチレン120mlに溶した液にバラフェ
ニレンジアミン0.4gを加え、室温で15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λmax
は塩化メチレン中で934nm,εは1.37×104、m.p.は69〜7
1℃であった。Example 2 Preparation of tetra-n-butylammonium bis [3-methoxy-4- (2-methoxyethoxy) -2'-chlorostilbenedithiolate] nickelate (complex 2) 1 g of complex 1 was dissolved in 120 ml of methylene chloride. 0.4 g of paraphenylenediamine was added to the above liquid and stirred at room temperature for 15 minutes, and then 1.6 g of tetra-n-butylammonium chloride was added,
Stir for another 40 minutes. Then the solvent was distilled off to obtain crude crystals,
This was recrystallized to obtain the target complex 2. Λmax of this thing
Is 934 nm in methylene chloride, ε is 1.37 × 10 4 , mp is 69 to 7
It was 1 ° C.
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−ヘプ
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〕ニッケレート 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−ヘプ
タトリエニル〕−3H−インドリウムヨージド0.3gをアセ
トン1.5ml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20ml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λmaxは756,925nm、εはそれぞれ2.82
×105、1.62×104、m.p.は168〜169℃であった。Example 3 1,3,3-Trimethyl-2- [7- (1,3,3-trimethyl-2-indolinylidene) -1,3,5-heptatrienyl] -3H-indolium bis [3-methoxy -4- (2-Methoxyethoxy) -2'-chlorostilbenedithiolate] nickelate 0.3 g of 1,3,3-trimethyl-2- [7- (1,3,3-trimethyl-2-indolinylidene) -1,3,5-heptatrienyl] -3H-indolium iodide and 1.5 ml of acetone A solution of 0.43 g of complex 2 dissolved in 5 ml of acetone was added to the solution, and the mixture was refluxed for 10 minutes and then filtered. 20 ml of methanol was added to the filtrate and cooled, and the precipitated crystals were collected by filtration. To do. The obtained crystals were boiled with methanol, cooled, and then collected by filtration to obtain the target complex 3. This product has λmax of 756,925 nm and ε of 2.82 in methylene chloride.
× 10 5 , 1.62 × 10 4 , mp was 168 to 169 ° C.
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。Example 4 In the same manner as in Example 1, the following representative complex was obtained.
〈作用〉 本発明になるニッケル錯体は塩化メチレン中で約750nm
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。 <Function> The nickel complex according to the present invention is about 750 nm in methylene chloride.
To a group of dyes having absorption in the infrared region from about 1200 nm, and each dye has a wide absorption band extending to about 300 nm.
たとえば錯体１ではλmaxは前記の如く、883nmであり、
短波長側吸収端は約750nmにあり、長波長側は約1050nm
にある。またε値は約１万から３万の範囲にある。For example, in complex 1, λmax is 883 nm as described above,
Short wavelength side absorption edge is about 750nm, long wavelength side is about 1050nm
It is in. The ε value is in the range of about 10,000 to 30,000.
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１と２の比較から、本発明になる
錯体１は公知錯体１に比べて、1,2ジクロルエタン（DC
E）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（EGME）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M
EK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。Table 1 shows a comparative example of the solubility of the complex of the present invention and the known complex. From the comparison of Nos. 1 and 2, the complex 1 of the present invention has 1,2 dichloroethane (DC
E) about 3 times, methyl ethyl ketone (MEK) about 16 times, ethylene glycol monoethyl ether (EGME) about 78 times.
2 times, it shows excellent solubility of about 69 times in ethanol. Further, from the comparison of Nos. 3 and 4, the complex 2 according to the present invention shows that DCE and M
EK shows almost the same solubility as the known complex 2, but EGME shows about 9 times the solubility, and EtOH shows about 14 times the solubility. The other complexes of the present invention show substantially similar improved solubility.
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。 The solubility was determined by a colorimetric method based on a fixed amount of the filtrate after keeping the solvent containing each sample in an ultrasonic generator for 3 hours and then filtering off excess sample crystals.
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１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１よりも
大きいことが判る。なおNK125は次の構造を有する。FIG. 1 is a diagram showing the quenching characteristics of the nickel complex of the present invention with respect to the cyanine dye, which was obtained by using a Shimadzu xenon fade tester in a methylene chloride solution of each sample.
This is a graph obtained by irradiating 1200 W of xenon light and measuring the absorbance at each time to obtain the residual rate. From the figure, it is understood that the complex 1 according to the present invention has an effect of greatly improving the light resistance of the cyanine dye (NK125), and this effect is larger than that of the known complex 1. NK125 has the following structure.
本発明の他の錯体も同様の効果を示す。 The other complexes of the present invention show similar effects.
〈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
ート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ィスク記
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ポリカー
ボネート樹脂系基板にも使用が可能となった。<Effect of the Invention> The nickel complex according to the present invention has absorption in the infrared region and is useful as an infrared absorbing dye. In addition, these complexes have improved solubility in not only ketone-based or halogen-based solvents but also alcohol-based solvents such as ethylene glycol monoethyl ether and ethanol. Therefore, it is useful as an optical disk recording medium as a stabilizer such as a cyanine dye. The improved solubility in alcoholic solvents has made it possible to use not only acrylic resin-based substrates but also polycarbonate resin-based substrates.
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。１はシアニン
色素NK125（5mg）、２はNK125（5mg）に錯体１（2.5m
g）を併用したもの、３はNK−125（5mg）に公知錯体１
（2.5mg）を併用したものをそれぞれ、塩化メチレン10m
lの溶液とし測定した。FIG. 1 is a diagram showing the effect of the nickel complex according to the present invention on the light resistance of a cyanine dye, in which the ordinate represents the residual ratio (%) of the dye and the abscissa represents the irradiation time (hr). 1 is cyanine dye NK125 (5mg), 2 is NK125 (5mg) complex 1 (2.5m
g) together with 3 is NK-125 (5 mg) known complex 1
(2.5 mg) combined with methylene chloride 10 m
l solution was measured.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 3/00 １０５ Ｇ０２Ｂ 5/22 8507−2Ｋ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C09K 3/00 105 G02B 5/22 8507-2K
Claims (1)
ハロゲン、Ｘは水素、アルコキシ基または−０−(CH2)n
−OR1を表し、ｍは１〜３の整数、ｎは１〜４の整数、
Ａはテトラアルキルアンモニウムカチオンまたはインド
ヘプタメチンシアニン色素のカチオン部を表す。）より
なる群の中から選ばれたニッケル錯体。1. A general formula (1) And general formula (2) (Wherein R 1 is hydrogen or a lower alkyl group, R 2 is hydrogen or halogen, X is hydrogen, an alkoxy group or -0- (CH 2 ) n
Represents -OR 1 , m is an integer of 1 to 3, n is an integer of 1 to 4,
A represents a tetraalkylammonium cation or a cation portion of an indoheptamethine cyanine dye. ) A nickel complex selected from the group consisting 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 JPH02264788A (en) | 1990-10-29 |
| JPH0745509B2 true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69824299T2 (en) | 1997-08-26 | 2004-10-21 | Kureha Chemical Ind Co Ltd | COPPER-CONTAINING PHOSPHORIC ACID ESTER DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF, SEMI-INFRARED ABORBER, AND SEMI-INFRARED ABSORBENT ACRYLIC RESIN PREPARATIONS |
| US6117370A (en) * | 1998-11-11 | 2000-09-12 | Nisshinbo Industries, Inc. | Near infrared absorption filter |
| 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 |
| JP4596682B2 (en) * | 2001-05-30 | 2010-12-08 | 株式会社Adeka | Optical filter |
| KR101201669B1 (en) * | 2009-12-03 | 2012-11-15 | (주)경인양행 | Near Infrared-Absorbing Compound of High Solubility and Excellent Durability, and Near Infrared-Absorbing Material Comprising the Same |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02264788A (en) | 1990-10-29 |
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