DE102004034866A1 - Mixtures of azo metal complexes as light-absorbing compounds in the information layer of optical data media - Google Patents

Abstract

Mixtures containing at least two different azo metal complexes, the ligands of formula DOLLAR F1 wherein DOLLAR AX · 1 · is S or NH, DOLLAR AX · 2 · and X · 3 · are independently CH or N, DOLLAR A being X 1 heteroaryl may be substituted by nonionic radicals, DOLLAR AR * 0 for NR 2 R 2 ', R 8 * or K * + An *, DOLLAR AR 2 * and R · 2 '· independently of one another are optionally substituted by hydroxyl, cyano or fluorine C¶1¶-C¶6¶-alkyl and DOLLAR AR · 2 · additionally can stand for hydrogen, DOLLAR AR · 3 · and R · 4 · independently are each C¶1¶-C¶4¶-alkyl optionally substituted by hydroxy, cyano, chloro, acetoxy or -COOR · 7 · or DOLLAR A NR · 3 · R · 4 · optionally substituted pyrrolidino, piperidino, morpholino, Piperazino or N-methyl-piperazino, DOLLAR AR · 5 · and R · 6 · are hydrogen or DOLLAR AR · 3 ·; R · 5 · and R · 4 ·; R 6 independently of one another are together a - (CH 2 2 3) ¶2¶ or - (CH¶2¶) ¶3¶ bridge, DOLLAR AR 8 * being optionally substituted by chlorine, C 1 - C 2-4 -alkoxy, in particular methoxy, cyano, nitro or aceto-amino-substituted 2-, 3- or 4-pyridyl, pyridine-N-oxide-2-, -3- or -4-yl, pyrimidine-2 or 4-yl, benzothiazol-2 or -6-yl, DOLLAR AK · + · is an optionally substituted by chlorine, C¶1¶-C¶4¶-alkoxy, in particular methoxy, cyano, nitro or aceto-amino-substituted radical of the formula DOLLAR F2, DOLLAR AR · 11 · is C¶1¶-C¶4¶-alkyl, in particular methyl, ethyl or benzyl and DOLLAR A An · + · is an anion.

Description

The The invention relates to mixtures of azo metal complexes, special Azometallkomplexe, a process for their preparation, as ligands the metal complexes acting azo compounds and their preparation, the azo compounds underlying coupling components and their manufacture as well as optical data storage, the metal complexes contained in their information layer.

The write-once optical disk using special light-absorbing substances or mixtures thereof are suitable especially for the use in high-density writable optical data storage, those with blue laser diodes, in particular GaN or SHG laser diodes (360 - 460 nm) work and / or for Use with DVD-R or CD-R discs with red (635 - 660 nm) or infrared (780-830 nm) laser diodes work, as well as the application of the above Dyes on a polymer substrate, in particular polycarbonate, by Spin coating or vapor deposition.

The once recordable compact disc (CD-R, 780 nm) experienced in the last Time a huge volume growth and represents the technically established System dar.

Current will be the next Generation optical data storage - the DVD - introduced to the market. By the use of shorter wavelength Laser radiation (635 to 660 nm) and higher numerical aperture NA can increases the storage density become. The recordable format in this case is the DVD-R.

Today, optical data storage formats, the blue laser diodes (base GaN, JP 08191171 or Second Harmonic Generation SHG JP 09050629 ) (360 nm to 460 nm) with high laser power. Recordable optical data storage will therefore also be used in this generation. The achievable storage density depends on the focusing of the laser spot in the information plane. The spot size scales with the laser wavelength λ / NA. NA is the numerical aperture of the objective lens used. To obtain the highest possible storage density, the use of the smallest possible wavelength λ is desirable. Are possible based on semiconductor laser diodes currently 390 nm.

In The patent literature is writeable based on dyes optical data storage described equally for CD-R and DVD-R systems are suitable (JP-A 11 043 481 and JP-A 10 181 206). It is for a high reflectivity and a high modulation height of the readout signal, as well as for a sufficient one Sensitivity to writing made use of the fact that the IR wavelength is 780 nm of the CD-R at the foot of the long-wave Flank of the absorption peak of the dye is the red wavelength 635 nm or 650 nm of the DVD-R at the foot of the short-wave edge of the absorption peak of the dye is. These Concept is disclosed in JP-A 02 557 335, JP-A 10 058 828, JP-A 06 336 086, JP-A 02 865 955, WO-A 09 917 284 and US-A 5 266 699 in the field 450 nm operating wavelength on the shortwave flank and the red and IR area on the long-wave flank of the absorption peak extended.

Next The above optical properties must be writable Information layer of light-absorbing organic substances one possible have amorphous morphology to describe the noise signal in writing or reading as possible to keep small. For this it is particularly preferred that in the application the substances by spin coating from a solution, by vapor deposition and / or sublimation during the subsequent overlaying with metallic or dielectric layers in vacuum crystallization the light-absorbing substances is prevented.

The Amorphous layer of light absorbing substances should preferably a high heat resistance own, otherwise other layers of organic or inorganic Material by sputtering or vapor deposition on the light-absorbing Information layer applied via diffusion to form blurred interfaces and thus the reflectivity unfavorable influence. About that In addition, a light-absorbing substance having too low heat distortion temperature at the interface to a polymer carrier diffuse in these and in turn affect the reflectivity unfavorable.

One too high vapor pressure of a light-absorbing substance can during mentioned above Sputtering or vapor deposition of further layers in a high vacuum sublime and thus the desired Reduce layer thickness. this leads to again to a negative influence on the reflectivity.

JP 11-310 728 describes an optical recording medium which has certain non-ionic Contains azo metal complexes in its information layer. These azo metal complexes contain azo dyes, which must contain at least 2 fluorine atoms. The azo dyes furthermore contain a grouping of the formula -NH-SO ₂ -Y, where Y is an alkyl or aryl radical. The optical data memory is suitable for a write and read laser wavelength of 630-660 nm.

task The invention accordingly provides the provision of suitable compounds, the high requirements (such as light stability, favorable signal-to-noise ratio, damage-free Application to the substrate material, etc.) for use in the information layer in a write once optical disk especially for high density Recordable optical data storage formats in a laser wavelength range from 340 to 680 nm.

surprisingly Way was found that as light-absorbing compounds mixtures of azo metal complexes the above requirement profile especially good fulfillment can.

worin
X¹ für S oder NH steht,
X² und X³ unabhängig voneinander für CH oder N stehen,
wobei der X¹ enthaltende Heterocyclus durch nichtionische Reste substituiert sein kann,
R⁰ für NR²R^2', R⁸ oder K⁺ An^- steht,
R² und R^2' unabhängig voneinander für gegebenenfalls durch Hydroxy, Cyano oder Fluor substituiertes C₁-C₆-Alkyl stehen und
R² zusätzlich für Wasserstoff stehen kann,
R³ und R⁴ unabhängig voneinander für gegebenenfalls durch Hydroxy, Cyano, Chlor, Acetoxy oder -COOR⁷ substituiertes C₁-C₄-Alkyl stehen oder
NR³R⁴ für gegebenenfalls substituiertes Pyrrolidino, Piperidino, Morpholino, Piperazino oder N-Methyl-piperazino steht,
R⁵ und R⁶ für Wasserstoff stehen oder
R³;R⁵ und R⁴;R⁶ unabhängig voneinander gemeinsam für eine -(CH₂)₂- oder -(CH₂)₃- Brücke stehen,
R⁸ für gegebenenfalls durch Chlor, C₁-C₄-Alkoxy, insbesondere Methoxy, Cyano, Nitro oder Acetamino substituiertes 2-, 3- oder 4-Pyridyl, Pyridin-N-oxid-2-, 3- oder 4-yl, Pyrimidin-2- oder -4-yl, Benzthiazol-2- oder -6-yl steht,
K⁺ für einen gegebenenfalls durch Chlor, C₁-C₄-Alkoxy, insbesondere Methoxy, Cyano, Nitro oder Acetamino substituierten Rest der Formel

steht,
R¹¹ für C₁-C₄-Alkyl, insbesondere Methyl, Ethyl oder Benzyl steht und
An^- für ein Anion steht.The invention therefore relates to mixtures containing at least two different azo metal complexes, the ligands of the formula

wherein
X ^{1 is} S or NH,
X ² and X ³ independently of one another are CH or N,
wherein the heterocycle containing X ¹ can be substituted by nonionic radicals,
R ^{0 is} NR ² R ^{2 '} , R ⁸ or K ⁺ An ^- stands,
R ² and R ^{2 'are} independently of each other optionally substituted by hydroxy, cyano or fluorine-substituted C ₁ -C ₆ alkyl and
R ^{2 can} additionally be hydrogen,
R ³ and R ⁴ independently of one another represent optionally C ₁ -C ₄ -alkyl substituted by hydroxy, cyano, chlorine, acetoxy or -COOR ⁷ or
NR ³ R ^{4 represents} optionally substituted pyrrolidino, piperidino, morpholino, piperazino or N-methyl-piperazino,
R ⁵ and R ^{6 are} hydrogen or
R ³ , R ⁵ and R ⁴ , R ⁶ independently of one another are together a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ - bridge,
R ^{8 represents} optionally substituted by chlorine, C ₁ -C ₄ alkoxy, in particular methoxy, cyano, nitro or acetamino substituted 2-, 3- or 4-pyridyl, pyridine-N-oxide-2-, 3- or 4-yl, Pyrimidine-2 or 4-yl, benzthiazol-2 or -6-yl,
K ^{+ is} an optionally substituted by chlorine, C ₁ -C ₄ alkoxy, in particular methoxy, cyano, nitro or aceto-amino-substituted radical of the formula

stands,
R ^{11 is} C ₁ -C ₄ -alkyl, in particular methyl, ethyl or benzyl, and
An ^{- stands} for an anion.

Preferred substituents of the heterocycle containing X ¹ are preferably trifluoromethyl, cyano, -COOR ⁷ , -C (= NH) OR ⁷ , -CONH ₂ , phenyl, chlorine, bromine, methyl, ethyl, phenyl, -SR ⁷ or -SO ₂ R ⁷ in question
wherein
R ^{7 is} C ₁ -C ₄ -alkyl, in particular methyl or ethyl.

Preference is given to mixtures according to the invention comprising at least one azometallic complex which carries at least one ligand of the formula (I) in which
X ^{1 is} NH and at least one different azometallic complex carrying at least one ligand of formula I, wherein
X ^{1 is} S and the remaining radicals have the above meanings.

und wenigstens einen davon verschiedenen Azometallkomplex, der wenigstens einen Liganden der Formel (IIIb) enthält

worin die Reste die oben beschriebenen Bedeutungen haben.Particular preference is given to mixtures comprising at least one azo metal complex which comprises at least one ligand of the formula (IIIa)

and at least one different azometallic complex containing at least one ligand of formula (IIIb)

wherein the radicals have the meanings described above.

Preferably, the X ² -containing heterocycle of the formula (IIIa) is unsubstituted or substituted by trifluoromethyl, cyano, -COOR ⁷ , -C (= NH) OR ⁷ , -CONH ₂ , -CONHR ⁷ or phenyl.

Preferably, the X ² -containing heterocycle of the formula (IIIb) is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, phenyl, -SR ⁷ or -SO ₂ R ⁷ .

besitzt und wenigstens einen davon verschiedenen Azometallkomplex, der wenigstens einen Liganden der Formel (XIV) und/oder (XV)

besitzt, worin
R⁰ für NR²R^2', R⁸ oder für einen Rest der Formel

steht,
R¹ für Methyl oder Benzyl steht,
R² und R^2' unabhängig voneinander für Methyl, Ethyl oder 2,2,2-Trifluorethyl stehen und
R² zusätzlich für Wasserstoff stehen kann,
R³ und R⁴ unabhängig voneinander für Methyl, Ethyl stehen oder
NR³R⁴ für Pyrrolidino, Piperidino, Morpholino, Piperazino oder N-Methyl-piperazino steht,
R⁵ und R⁶ für Wasserstoff stehen oder
R³;R⁵ und R⁴;R⁶ unabhängig voneinander gemeinsam für eine -(CH₂)₂- oder -(CH₂)₃- Brücke stehen,
R⁷ für Methyl oder Ethyl steht,
R⁸ für 2-, 3- oder 4-Pyridyl steht und
R⁹ für Wasserstoff, Methyl, Chlor oder Brom steht,
R¹⁰ für Trifluormethyl steht,
R¹¹ für Methyl, Ethyl oder Benzyl steht und
An^- für ein Anion steht,
wobei die Reste in Liganden (XI) bis (XV) nicht die gleiche Bedeutung haben müssen.Very particular preference is given to mixtures comprising at least one azo metal complex which has at least one ligand of the formula (XI), (XII) and / or (XIII)

and at least one different azometallic complex containing at least one ligand of formula (XIV) and / or (XV)

possesses, in which
R ⁰ for NR ² R ^{2 '} , R ⁸ or for a radical of the formula

stands,
R ^{1 is} methyl or benzyl,
R ² and R ^{2 'are} independently methyl, ethyl or 2,2,2-trifluoroethyl and
R ^{2 can} additionally be hydrogen,
R ³ and R ^{4 are} independently methyl, ethyl or
NR ³ R ^{4 is} pyrrolidino, piperidino, morpholino, piperazino or N-methyl-piperazino,
R ⁵ and R ^{6 are} hydrogen or
R ³ , R ⁵ and R ⁴ , R ⁶ independently of one another are together a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ - bridge,
R ^{7 is} methyl or ethyl,
R ^{8 is} 2-, 3- or 4-pyridyl and
R ^{9 is} hydrogen, methyl, chlorine or bromine,
R ^{10 is} trifluoromethyl,
R ^{11 is} methyl, ethyl or benzyl and
An ^{- stands} for an anion,
where the radicals in ligands (XI) to (XV) need not have the same meaning.

sowie die Mischung der Isomeren der Formeln (XII) und (XIIa) gemeint.With formula (XII) is here and further down, z. In formula (IIb), also the isomer of the formula

and the mixture of isomers of formulas (XII) and (XIIa).

und

sowie die Mischung von 2 oder 3 dieser Isomeren der Formeln (XIII), (XIIIa) und (XIIIb) gemeint.With formula (XIII) are here and further down, z. B. in formula (IIc), and the isomers of the formulas

and

and the mixture of 2 or 3 of these isomers of formulas (XIII), (XIIIa) and (XIIIb).

The Azometallkomplexe lie in a preferred embodiment as 1: 1 or 1: 2 metal: Azo complexes before, particularly preferred as 1: 2 metal: azo complexes.

Clear preferred are those azometallic complexes which are two identical or different, in particular two identical ligands of the formula (I) included. These these are two different ligands, and so are the statistical ones Meant mixtures of the complexes obtainable from ligands and metal.

entsprechen, worin die beiden Liganden (I) unabhängig voneinander die oben angegebene Bedeutung der Liganden der Formeln (I), insbesondere (IIIa), (IIIb) oder (XI) bis (XV) besitzen und
M für ein Metall steht.Preferred are those Azometallkomplexe, which are characterized in that they of the formula (Ia)

in which the two ligands (I) independently of one another have the abovementioned meaning of the ligands of the formulas (I), in particular (IIIa), (IIIb) or (XI) to (XV), and
M stands for a metal.

When preferred metals for the arometallic complexes come divalent transition metals, in particular Cu, Ni, Co, Zn, Pd, in question. Preferably, the metals are Cu, Ni and Co. Particularly preferred is Ni.

Especially preferred are the azo metal complexes, the ligands of the formulas (IIIa) or (IIIb), especially (XI), (XIV) and (XV).

R¹ für Methyl,
R² für Methyl oder 2,2,2-Trifluorethyl,
R^2' für Wasserstoff oder Methyl,
R³ und R⁴ für Ethyl und R⁵ und R⁶ für Wasserstoff oder
NR³R⁴ für Pyrrolidino und R⁵ und R⁶ für Wasserstoff oder
R³;R⁵ für eine -CH₂-CH₂-Brücke und R⁴ für Methyl oder Ethyl und R⁶ für Wasserstoff oder
R³;R⁵ und R⁴;R⁶ für eine -CH₂-CH₂-CH₂-Brücke,
R⁸ für 2- oder 3-Pyridyl,
R⁹ für Wasserstoff, Methyl oder Brom;
R¹¹ für Methyl und
An^- für ein Anion.In formulas (XI), (XIV) and (XV) are preferred
R ^{0 is} NR ² R ^{2 '} , R ⁸ or a radical of the formula

R ^{1 is} methyl,
R ^{2 is} methyl or 2,2,2-trifluoroethyl,
R ^{2 'is} hydrogen or methyl,
R ³ and R ^{4 are} ethyl and R ⁵ and R ^{6 are} hydrogen or
NR ³ R ⁴ for pyrrolidino and R ⁵ and R ⁶ for hydrogen or
R ³ , R ^{5 is} a -CH ₂ -CH ₂ -bridge and R ^{4 is} methyl or ethyl and R ^{6 is} hydrogen or
R ³ , R ⁵ and R ⁴ ; R ^{6 represents} a -CH ₂ -CH ₂ -CH ₂ -bridge,
R ^{8 is} 2- or 3-pyridyl,
R ^{9 is} hydrogen, methyl or bromine;
R ¹¹ for methyl and
An ^- for an anion.

In the formulas (XI), (XIV) and (XV), particularly preferable
R ⁰ for NR ² R ^{2 '} ,
R ^{1 is} methyl,
R ² and R ^{2 'are} methyl,
R ³ and R ^{4 are} ethyl and R ⁵ and R ^{6 are} hydrogen or
R ³ ; R ⁵ and R ⁴ ; R ^{6 represents} a -CH ₂ -CH ₂ -CH ₂ -bridge and
R ^{9 is} methyl or bromine.

In the formulas (XI), (XIV) and (VX) are also particularly preferred
R ^{0 is} 3-pyridyl,
R 'for methyl,
R ² and R ^{2 'are} methyl,
R ³ and R ^{4 are} ethyl and R ⁵ and R ^{6 are} hydrogen or
R ³ ; R ⁵ and R ⁴ ; R ^{6 represents} a -CH ₂ -CH ₂ -CH ₂ -bridge and
R ^{9 is} methyl or bromine.

R¹ für Methyl,
R² und R^2' für Methyl,
R³ und R⁴ für Ethyl und R⁵ und R⁶ für Wasserstoff oder
R³;R⁵ und R⁴;R⁶ für eine -CH₂-CH₂-CH₂-Brücke,
R⁹ für Methyl oder Brom,
R¹¹ für Methyl und
An^- für ein Anion.In the formulas (XI), (XIV) and (XV) are also particularly preferred
R ^{0 is} a radical of the formula

R ^{1 is} methyl,
R ² and R ^{2 'are} methyl,
R ³ and R ^{4 are} ethyl and R ⁵ and R ^{6 are} hydrogen or
R ³ , R ⁵ and R ⁴ ; R ^{6 represents} a -CH ₂ -CH ₂ -CH ₂ -bridge,
R ^{9 is} methyl or bromine,
R ¹¹ for methyl and
An ^- for an anion.

worin
R⁰ für eine der folgenden Formeln steht:

wobei An^- für eine Anion steht.Preferred mixtures of azo metal complexes are those which contain nickel complexes of the formula (Ia) with the following ligands:

wherein
R ^{0 is} one of the following formulas:

where An ^{- is} an anion.

Suitable anions An ^- are all monovalent anions or one equivalent of a polyvalent anion or an equivalent of an oligomeric or polymeric anion in question. Preferably, they are colorless anions. Suitable anions are, for example, chloride, bromide, iodide, nitrate, tetrafluoroborate, perchlorate, Hexafluorosilicate, hexafluorophosphate, methosulfate, ethosulfate, C ₁ - to C ₁₀ -alkanesulfonate, C ₁ - to C ₁₀ -perfluoroalkanesulfonate, (CF ₃ SO ₂ ) ₂ N ^- , if appropriate by chlorine, hydroxyl, C ₁ - to C ₄ - Alkoxy-substituted C ₁ - to C ₁₀ alkanoate, optionally substituted by nitro, cyano, hydroxy, C ₁ - to C ₂₅ -alkyl, perfluoro-C ₁ - to C ₄ -alkyl, C ₁ - to C ₄ -alkoxycarbonyl or chlorine-substituted Benzenesulfonate or naphthalene or biphenylsulfonate, benzene or naphthalene optionally substituted by nitro, cyano, hydroxy, C ₁ - to C ₄ -alkyl, C ₁ - to C ₄ -alkoxy, C ₁ - to C ₄ -alkoxycarbonyl or chlorine-substituted or biphenyl disulfonate, benzoate optionally substituted by nitro, cyano, C ₁ to C ₄ alkyl, C ₁ to C ₄ alkoxy, C ₁ to C ₄ alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl, the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate , Tetraphenylborate, cyanotriphenylborate, tetra-C ₁ - to C ₂₀ -alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido-and ecaborate (1-) or (2-) optionally substituted on the B and / or C atoms by one or two C ₁ to C ₁₂ alkyl or phenyl groups, dodecahydro-dicarbadodecaborate (2-) or BC ₁ - to C ₁₂ -alkyl-C-phenyl-dodecahydrodicarbadodecaborate (1-), polystyrenesulfonate, poly (meth) acrylate, polyallylsulfonate.

Prefers are bromide, iodide, tetrafluoroborate, perchlorate, hexafluorophosphate, Methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, Dodecylbenzenesulfonate, tetradecanesulfonate, polystyrenesulfonate.

Further, as anions ^, all monovalent anions or one equivalent of a polyvalent anion of a dye can be used. Preferably, the anionic dye An ^{- has} a similar absorption spectrum as the cationic azometal salt. Suitable examples are anionic azo dyes, anthraquinone dyes, methine dyes, porphyrins, phthalocyanines, subphthalocyanines, cyanines, merocyanines, rhodamines, metal complexes and oxonols. Suitable rhodamines as anions are known, for example, from DE-A 101 36 064. Suitable cyanines as anions are known, for example, from US 2002/0022104. Suitable metal complexes as anions are known, for example, from WO 03/098618. Suitable oxonols as anions are known, for example, from EP-A 1 253 148.

worin
R¹⁰¹ und R¹⁰³ unabhängig voneinander für Wasserstoff, Methyl oder Ethyl stehen,
R¹⁰² und R¹⁰⁴ unabhängig voneinander für einen durch Sulfo oder Carboxy substituierten Phenyl-, Naphthyl-, Benzthiazolyl- oder Benzoxazolyl-Rest stehen, die durch Chlor, Hydroxy, Methyl, Methoxy oder Methylthio substituiert sein können,
R¹⁰⁵, R¹⁰⁶, R¹⁰⁸ und R¹⁰⁹ für unabhängig voneinander Wasserstoff, Methyl oder Methoxy stehen oder
R¹⁰¹ R¹⁰⁵, R¹⁰²; R¹⁰⁶, R¹⁰³; R¹⁰⁸ und R¹⁰⁴; R¹⁰⁹ unabhängig voneinander für -(CH₂)₂-, -(CH₂)₃-, -C(CH₃)₂-CH₂-CH(CH₃)- oder -O(CH₂)₂- stehen und
R¹⁰⁷ für Wasserstoff oder Sulfo steht.Preference is given to metal complexes of the formulas (Ia) with ligands of the formulas (XI) to (XV), in particular those metal complexes of the formulas (IIa) to (IIe) in which R ^{0 is} K ⁺ An ^- , where
An ^{- stands} for iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate or the anion or one equivalent of an anion of a rhodamine, oxonol, merocyanine, cyanine or metal complex dye
and K ⁺ and the other radicals are as defined above. Suitable rhodamine dyes are, for. For example, those of the formula (C)

wherein
R ¹⁰¹ and R ¹⁰³ independently of one another represent hydrogen, methyl or ethyl,
R ¹⁰² and R ¹⁰⁴ independently of one another represent a sulfo or carboxy-substituted phenyl, naphthyl, benzthiazolyl or benzoxazolyl radical which may be substituted by chlorine, hydroxyl, methyl, methoxy or methylthio,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁸ and R ^{109 are} independently hydrogen, methyl or methoxy or
R ¹⁰¹ R ¹⁰⁵ , R ¹⁰² ; R ¹⁰⁶ , R ¹⁰³ ; R ¹⁰⁸ and R ¹⁰⁴ ; R ¹⁰⁹ independently of one another are - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) - or -O (CH ₂ ) ₂ - and
R ^{107 is} hydrogen or sulfo.

worin
die Ringe B und C für einen fünf- oder sechsgliedrigen, carbocyclischen oder heterocyclischen Ring stehen.Suitable oxonol dyes are, for. B. those of the formula (CI)

wherein
the rings B and C are a five- or six-membered, carbocyclic or heterocyclic ring.

Preferably are identical in formula (CI) B and C.

wobei von dem mit * gekennzeichnete C-Atom die Doppelbindung zum Rest der Formel (CI) ausgeht,
und der Ring C zusammen mit den beiden C-Atomen und dem Sauerstoffatom für einen Rest der Formeln

wobei von dem mit ~ gekennzeichneten C-Atom die Einfachbindung zum Rest der Formel (CI) ausgeht,
worin
R¹¹¹ und R¹¹² unabhängig voneinander für Wasserstoff oder Methyl stehen,
R¹¹³ für Methyl oder Trifluormethyl steht,
R¹¹⁴ für Cyano, Methoxycarbonyl oder Ethoxycarbonyl steht,
R¹¹⁵ für Phenyl, Chlorphenyl oder Tolyl steht.Preferably, the ring B together with the two C atoms and the oxygen atom are a radical of the formulas

where the double bond of the C atom denoted by * is the radical of the formula (CI),
and the ring C together with the two carbon atoms and the oxygen atom for a group of the formulas

where the single bond of the carbon atom marked ~ represents the remainder of the formula (CI),
wherein
R ¹¹¹ and R ¹¹² independently of one another represent hydrogen or methyl,
R ^{113 is} methyl or trifluoromethyl,
R ^{114 is} cyano, methoxycarbonyl or ethoxycarbonyl,
R ^{115 is} phenyl, chlorophenyl or tolyl.

worin
Y¹⁰¹ und Y¹⁰² unabhängig voneinander für -O- oder -COO- stehen,
M¹⁰¹ für ein zwei- oder dreiwertiges Metall steht,
die Ringe H für einen Benzolring oder für einen fünf- oder sechsgliedrigen, carbocyclischen oder heterocyclischen Ring stehen, die benzanelliert und/oder durch nichtionische Reste, COOH oder SO₃H substituiert sein können.Suitable metal complex dyes are, for. Eg those of the formula (CII)

wherein
Y ¹⁰¹ and Y ¹⁰² independently of one another represent -O- or -COO-,
M ^{101 is} a divalent or trivalent metal,
the rings H stand for a benzene ring or for a five- or six-membered, carbocyclic or heterocyclic ring which can be benzanellated and / or substituted by nonionic radicals, COOH or SO ₃ H.

wobei von dem mit ~ gekennzeichneten C-Atom die Einfachbindung zum Rest der Verbindung (CII) ausgeht,
worin
R¹¹¹ und R¹¹² unabhängig voneinander für Wasserstoff oder Methyl stehen,
R¹¹³ für Methyl oder Trifluormethyl steht,
R¹¹⁵ für Phenyl, Chlorphenyl oder Tolyl steht.
M¹⁰¹ steht vorzugsweise für Ni, Co, Cr, Fe, Cu.Preferably, the rings H together with the two carbon atoms and Y ^{102 are} a radical of the formulas

where the single bond of the carbon atom marked ~ represents the remainder of the compound (CII),
wherein
R ¹¹¹ and R ¹¹² independently of one another represent hydrogen or methyl,
R ^{113 is} methyl or trifluoromethyl,
R ^{115 is} phenyl, chlorophenyl or tolyl.
M ¹⁰¹ is preferably Ni, Co, Cr, Fe, Cu.

worin
Y¹⁰³ und Y¹⁰⁴ unabhängig voneinander für S, C(CH₃)₂ oder -CH=CH- stehen,
R¹³¹ und R¹³² unabhängig voneinander für -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^- stehen,
R¹³³ und R¹³⁴ unabhängig voneinander für Wasserstoff, einen nichtionischen Rest, -COO^- oder -SO₃ ^- stehen,
die Benzolringe D und E unabhängig voneinander benzanneliert sein können und
n für eine ganze Zahl von 2 bis 5 steht.Suitable cyanine dyes are, for. For example, those of the formula (CIII)

wherein
Y ¹⁰³ and Y ¹⁰⁴ independently represent S, C (CH ₃ ) ₂ or -CH = CH-,
R ¹³¹ and R ¹³² independently of one another are - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- ,
R ¹³³ and R ¹³⁴ independently of one another represent hydrogen, a nonionic radical, -COO ^- or -SO ₃ ^- ,
the benzene rings D and E can be independently benzannelated and
n is an integer from 2 to 5.

worin
der Ring G für einen Rest der Formeln

wobei von dem mit * gekennzeichneten C-Atom die Doppelbindung zum Rest der Verbindung (CIV) ausgeht,
steht,
Y¹⁰⁵ für S, C(CH₃)₂ oder -CH=CH- steht,
R¹³⁵ für Methyl, Ethyl, Benzyl, -(CH₂)_n- COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^- steht,
R¹³⁶ für Wasserstoff, einen nichtionischen Rest, -COO^- oder -SO₃ ^- steht,
der Benzolring F benzanneliert sein kann,
R¹²¹ und R¹²² unabhängig voneinander für Wasserstoff, Methyl oder -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^- stehen,
R¹²³ für Methyl oder Trifluormethyl steht,
R¹²⁴ für Cyano, Methoxycarbonyl oder Ethoxycarbonyl steht,
R¹²⁵ für Phenyl, Chlorphenyl oder Tolyl steht und
n für eine ganze Zahl von 2 bis 5 steht,
wobei wenigstens einer der Reste R¹³⁵, R¹²¹ und R¹²² für -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^-, vorzugsweise für -(CH₂)_n-SO₃ ^- steht.Suitable merocyanine dyes are, for. For example, those of the formula (CIV)

wherein
the ring G for a remainder of the formulas

where the double bond of the carbon atom marked with * starts from the remainder of the compound (CIV),
stands,
Y ^{105 is} S, C (CH ₃ ) ₂ or -CH = CH-,
R ^{135 represents} methyl, ethyl, benzyl, - (CH ₂ ) _n --COO ^- , - (CH ₂ ) _n --SO ₃ ^- or - (CH ₂ ) _n --O ^- SO ₃ ^- ,
R ^{136 is} hydrogen, a nonionic radical, -COO ^- or -SO ₃ ^- ,
the benzene ring F can be benzanelated,
R ¹²¹ and R ¹²² independently of one another represent hydrogen, methyl or - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- ,
R ^{123 is} methyl or trifluoromethyl,
R ^{124 is} cyano, methoxycarbonyl or ethoxycarbonyl,
R ^{125 is} phenyl, chlorophenyl or tolyl and
n is an integer from 2 to 5,
wherein at least one of R ¹³⁵ , R ¹²¹ and R ^{122 is} - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- , preferably - (CH ₂ ) _n -SO ₃ ^- stands.

worin
der Ring G für einen Rest der Formeln

wobei von dem mit * gekennzeichneten C-Atom die Doppelbindung zum Rest der Formel (CV) ausgeht,
steht,
Y¹⁰⁶ für O, S oder -CH=CH- steht,
Y¹⁰⁷ für N, CH oder C-CN steht,
R¹²⁶ für Wasserstoff, Methyl, Ethyl, Propyl oder Phenyl steht,
R¹²⁷ für Wasserstoff, Methyl, Ethyl, Propyl, Butyl, -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^- steht,
R¹²⁸ für Wasserstoff, Methyl, Ethyl, Propyl, Butyl oder Phenyl steht,
R¹²¹ und R¹²² unabhängig voneinander für Wasserstoff, Methyl oder -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^- stehen,
R¹²³ für Methyl oder Trifluormethyl steht,
R¹²⁴ für Cyano, Methoxycarbonyl oder Ethoxycarbonyl steht,
R¹²⁵ für Phenyl, Chlorphenyl oder Tolyl steht und
n für eine ganze Zahl von 3 bis 5 steht,
wobei wenigstens einer der Reste R¹²⁷, R¹²¹ und R¹²² für -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^-; vorzugsweise für -(CH₂)_n-SO₃ ^- steht.Also suitable merocyanine dyes are, for. B. those of formula (CV)

wherein
the ring G for a remainder of the formulas

where the double bond to the rest of the formula (CV) starts from the carbon atom marked with *,
stands,
Y ^{106 is} O, S or -CH = CH-,
Y ^{107 is} N, CH or C-CN,
R ^{126 is} hydrogen, methyl, ethyl, propyl or phenyl,
R ^{127 is} hydrogen, methyl, ethyl, propyl, butyl, - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- ,
R ^{128 is} hydrogen, methyl, ethyl, propyl, butyl or phenyl,
R ¹²¹ and R ¹²² independently of one another represent hydrogen, methyl or - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- ,
R ^{123 is} methyl or trifluoromethyl,
R ^{124 is} cyano, methoxycarbonyl or ethoxycarbonyl,
R ^{125 is} phenyl, chlorophenyl or tolyl and
n is an integer from 3 to 5,
wherein at least one of R ¹²⁷ , R ¹²¹ and R ^{122 is} - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- ; preferably represents - (CH ₂ ) _n -SO ₃ ^- stands.

worin
X¹⁴¹ für O oder S steht,
X¹⁴² für CR¹⁵⁰ oder N steht,
R¹⁴³ für Wasserstoff, C₁- bis C₆-Alkyl, Halogen, Hydroxy oder C₆- bis C₁₀-Aryl steht,
R¹⁴¹ und R¹⁴² unabhängig voneinander für Wasserstoff, C₁- bis C₆-Alkyl, C₅- bis C₇-Cycloalkyl, C₆- bis C₁₀-Aryl oder C₇- bis C₁₅-Aralkyl stehen oder
NR¹⁴¹R¹⁴² für Pyrrolidino, Morpholino, Piperazino oder Piperidino stehen,
R¹⁵⁰ für Wasserstoff, Cyano, C₁- bis C₆-Alkyl, Halogen oder C₆- bis C₁₀-Aryl steht,
Y¹⁰⁸ für N oder C-R¹⁵⁸ steht,
R¹⁵⁸ für Wasserstoff oder Cyano steht,
Q für einen Rest der Formeln

worin
X¹⁰³ für O oder S steht,
X¹⁰⁴ für CR¹⁵¹ oder N steht,
R¹⁴⁶ für Wasserstoff, C₁- bis C₆-Alkyl, Halogen, Hydroxy oder C₆- bis C₁₀-Aryl steht oder
R¹⁴³ und R¹⁴⁶ eine -O- oder -C(CH₃)₂-Brücke bilden,
R¹⁴⁴ und R¹⁴⁵ unabhängig voneinander für Wasserstoff, C₁- bis C₆-Alkyl, C₅- bis C₇-Cycloalkyl, C₆- bis C₁₀-Aryl oder C₇- bis C₁₅-Aralkyl stehen oder
NR¹⁴⁴R¹⁴⁵ für Pyrrolidino, Morpholino, Piperazino oder Piperidino steht,
R¹⁵¹ für Wasserstoff, Cyano, C₁- bis C₆-Alkyl, Halogen oder C₆- bis C₁₀-Aryl steht,
X¹⁰⁵ für Stickstoff steht oder
X¹⁰⁵-R¹⁴⁷ für S steht,
X¹⁰⁶ für O, S, N-R¹⁵⁹,CR¹⁶⁰ oder CR¹⁶⁰R¹⁶¹ steht,
Y¹⁰⁹ für N oder C-R¹⁵⁸ steht,
R¹⁴⁷ und R¹⁵⁹ abhängig voneinander für C₁- bis C₁₆-Alkyl, C₃- bis C₆-Alkenyl, C₅- bis C₇-Cycloalkyl oder C₇- bis C₁₆-Aralkyl stehen,
R¹⁶⁰ und R¹⁶¹ unabhängig voneinander für Wasserstoff oder Methyl stehen,
S zusammen mit X¹⁰⁵, X¹⁰⁶ und dem dazwischen gebundenen C-Atom für einen fünf- oder sechsgliedrigen aromatischen oder quasiaromatischen oder teilhydrierten heterocyclischen Ring steht, der 1 bis 4 Heteroatome enthalten und/oder benz- oder naphthanelliert und/oder durch nichtionische Reste substituiert sein kann,
R¹⁵⁴ und R¹⁵⁵ unabhängig voneinander für Wasserstoff, C₁- bis C₁₆-Alkyl, C₄- bis C₇-Cycloalkyl, C₇- bis C₁₆-Aralkyl, C₆- bis C₁₀-Aryl oder einen heterocyclischen Rest stehen oder
NR¹⁵⁴R¹⁵⁵ für einen fünf- oder sechsgliedrigen, über N angebundenen gesättigten Ring stehen, der zusätzlich ein N oder O enthalten kann und/oder durch nichtionische Reste substituiert sein kann,
R¹⁵⁶ und R^156' unabhängig voneinander für Wasserstoff, C₁- bis C₁₆-Alkyl, C₁- bis C₁₆-Alkoxy oder Halogen stehen oder
R¹⁵⁶; R¹⁵⁴ und/oder R^156'; R¹⁵⁵ eine zwei- oder dreigliedrige Brücke bilden, die ein O oder N enthalten kann und/oder durch nichtionische Reste substituiert sein kann,
R¹⁵⁷ für Wasserstoff, C₁- bis C₁₆-Alkyl, C₁- bis C₁₆-Alkoxy, Halogen, Cyano, C₁- bis C₄-Alkoxycarbonyl, O-CO-R¹⁶², NR¹⁶³-CO-R¹⁶², O-SO₂-R¹⁶² oder NR¹⁶³-SO₂-R¹⁶² steht,
R¹⁶² für Wasserstoff, C₁- bis C₁₆-Alkyl, C₄- bis C₇-Cycloalkyl, C₇- bis C₁₆-Aralkyl, C₁- bis C₁₆-Alkoxy, Mono- oder Bis-C₁- bis C₁₆-Alkylamino, C₆- bis C₁₀-Aryl, C₆- bis C₁₀-Aryloxy, C₆- bis C₁₀-Arylamino oder einen heterocyclischen Rest steht und
R¹⁶³ für Wasserstoff oder C₁- bis C₄-Alkyl steht,
wobei
wenigstens zwei der Reste R¹⁴¹, R¹⁴², R¹⁴⁴, R¹⁴⁵, R¹⁴⁷, R¹⁵⁴ und R¹⁵⁵ für -(CH₂)_n-COO^-, -(CH₂)_n-SO₃ ^- oder -(CH₂)_n-O-SO₃ ^-, vorzugsweise für -(CH₂)_n-SO₃ ^- stehen und für
n für eine ganze Zahl von 2 bis 5 steht.Also suitable anionic methine dyes are, for. B. those of the formula (CVI)

wherein
X ^{141 stands} for O or S,
X ^{142 is} CR ¹⁵⁰ or N,
R ^{143 is} hydrogen, C ₁ - to C ₆ -alkyl, halogen, hydroxy or C ₆ - to C ₁₀ -aryl,
R ¹⁴¹ and R ¹⁴² independently of one another are hydrogen, C ₁ - to C ₆ -alkyl, C ₅ - to C ₇ -cycloalkyl, C ₆ - to C ₁₀ -aryl or C ₇ - to C ₁₅ -aralkyl, or
NR ¹⁴¹ R ^{142 represents} pyrrolidino, morpholino, piperazino or piperidino,
R ^{150 is} hydrogen, cyano, C ₁ - to C ₆ -alkyl, halogen or C ₆ - to C ₁₀ -aryl,
Y ^{108 stands} for N or CR ¹⁵⁸ ,
R ^{158 is} hydrogen or cyano,
Q for a remainder of the formulas

wherein
X ^{103 is} O or S,
X ^{104 is} CR ¹⁵¹ or N,
R ^{146 is} hydrogen, C ₁ - to C ₆ -alkyl, halogen, hydroxy or C ₆ - to C ₁₀ -aryl or
R ¹⁴³ and R ^{146 form} an -O- or -C (CH ₃ ) ₂ bridge,
R ¹⁴⁴ and R ¹⁴⁵ independently of one another are hydrogen, C ₁ - to C ₆ -alkyl, C ₅ - to C ₇ -cycloalkyl, C ₆ - to C ₁₀ -aryl or C ₇ - to C ₁₅ -aralkyl, or
NR ¹⁴⁴ R ^{145 represents} pyrrolidino, morpholino, piperazino or piperidino,
R ^{151 is} hydrogen, cyano, C ₁ - to C ₆ -alkyl, halogen or C ₆ - to C ₁₀ -aryl,
X ^{105 is} nitrogen or
X ¹⁰⁵ -R ¹⁴⁷ stands for S,
X ^{106 is} O, S, NR ¹⁵⁹ , CR ¹⁶⁰ or CR ¹⁶⁰ R ¹⁶¹ ,
Y ^{109 stands} for N or CR ¹⁵⁸ ,
R ¹⁴⁷ and R ¹⁵⁹ are each independently C ₁ - to C ₁₆ -alkyl, C ₃ - to C ₆ -alkenyl, C ₅ - to C ₇ -cycloalkyl or C ₇ - to C ₁₆ -aralkyl,
R ¹⁶⁰ and R ¹⁶¹ independently of one another represent hydrogen or methyl,
S together with X ¹⁰⁵ , X ¹⁰⁶ and the C atom bonded between them represents a five- or six-membered aromatic or quasi-aromatic or partially hydrogenated heterocyclic ring containing 1 to 4 heteroatoms and / or benzo or naphthanellated and / or substituted by nonionic groups can be,
R ¹⁵⁴ and R ¹⁵⁵ independently of one another are hydrogen, C ₁ - to C ₁₆ -alkyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to C ₁₆ -aralkyl, C ₆ - to C ₁₀ -aryl or a heterocyclic radical or
NR ¹⁵⁴ R ^{155 is} a five- or six-membered, N-connected saturated ring which may additionally contain an N or O and / or may be substituted by nonionic radicals,
R ¹⁵⁶ and R ^{156 '} independently of one another are hydrogen, C ₁ - to C ₁₆ -alkyl, C ₁ - to C ₁₆ -alkoxy or halogen or
R ¹⁵⁶ ; R ¹⁵⁴ and / or R ^{156 '} ; R ^{155 forms} a two- or three-membered bridge which may contain an O or N and / or may be substituted by nonionic radicals,
R ^{157 is} hydrogen, C ₁ - to C ₁₆ -alkyl, C ₁ - to C ₁₆ -alkoxy, halogen, cyano, C ₁ - to C ₄ -alkoxycarbonyl, O-CO-R ¹⁶² , NR ¹⁶³ -CO-R ¹⁶² , O-SO ₂ -R ¹⁶² or NR ¹⁶³ -SO ₂ -R ¹⁶² ,
R ^{162 is} hydrogen, C ₁ - to C ₁₆ -alkyl, C ₄ - to C ₇ -cycloalkyl, C ₇ - to C ₁₆ -aralkyl, C ₁ - to C ₁₆ -alkoxy, mono- or bis-C ₁ - to C ₁₆ alkylamino, C ₆ - to C ₁₀ aryl, C ₆ - to C ₁₀ aryloxy, C ₆ - to C ₁₀ arylamino or a heterocyclic radical and
R ^{163 is} hydrogen or C ₁ - to C ₄ -alkyl,
in which
at least two of R ¹⁴¹ , R ¹⁴² , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁷ , R ¹⁵⁴ and R ^{155 are} - (CH ₂ ) _n -COO ^- , - (CH ₂ ) _n -SO ₃ ^- or - (CH ₂ ) _n -O-SO ₃ ^- , preferably for - (CH ₂ ) _n -SO ₃ ^- and for
n is an integer from 2 to 5.

nonionic Radicals are, for example, halogen, alkyl, alkenyl, aralkyl, aryl, Alkoxy, alkylthio, hydroxy, amino, alkylamino, dialkylamino, cyano, Nitro, alkoxycarbonyl, alkylamino or dialkylaminocarbonyl, alkanoyl, Aroyl, alkylsulfonyl, arylsulfonyl.

Especially Preferred mixtures of Azometallkomplexen are those which have a Nickel complexes of the formula (Ia) with two identical ligands of the formulas (XIa) to (XId) and a nickel complexes of the formula (Ia) with two Ligands of the formulas (XIVa) to (XIVd) included.

Also particularly preferred mixtures of azo metal complexes are those the one nickel complexes of the formula (Ia) with two identical ligands of the formulas (XIa) to (XId) and a nickel complexes of the formula (Ia) with two identical ligands of the formulas (XVa) to (XVl).

All particularly preferred mixtures of azo metal complexes are those the one nickel complexes of the formula (Ia) with two identical ligands of the formula (XIa) and a nickel complex of the formula (Ia) with two same ligand of the formula (XIVa) included.

Also Very particularly preferred mixtures of Azometallkomplexen are those which have a nickel complex of the formula (Ia) with two identical Ligands of the formula (XIa) and a nickel complex of the formula (Ia) with two identical ligands of the formulas (XVa), (XVe), XVi).

wobei An^- für ein Anion steht.R ⁰ in these particularly and very particularly preferred mixtures of azo metal complexes preferably stands for one of the following formulas:

where An ^{- stands} for an anion.

C ₁ -C ₆ -alkyl radicals are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, which are substituted by the radicals which have been added above may be substituted. Examples of such substituted alkyl radicals are: perfluorinated methyl, perfluorinated ethyl, 2,2-trifluoroethyl, 3,3,3-trifluoroethyl, perfluorobutyl, cyanoethyl, methoxyethyl, chloroethyl, acetoxyethyl, methoxycarbonylethyl.

Also Preferred are azo metal complexes with ligands of the formula (XI) to (XV), the latter having no fluorine atoms.

worin M und die Reste der jeweiligen Azoliganden unabhängig voneinander die oben genannte Bedeutung haben. Im Rahmen dieser Anmeldung wird davon ausgegangen, dass die jeweiligen Formeln (IIa) bis (IIe) Unterformeln von (Ia) charakterisieren.The particularly preferred azo metal complexes of the formula (Ia) each have 2 ligands, as can be taken from the formulas (XI) to (XV). It is assumed that they are in the form of the formulas (IIa) to (IIe):

wherein M and the radicals of the respective azoligands independently of one another have the abovementioned meaning. In the context of this application it is assumed that the respective formulas (IIa) to (IIe) characterize sub-formulas of (Ia).

The mixtures according to the invention can of course, in addition to the mixture of at least two azo metal complexes further org. contain light-absorbing compounds. Preferably consist the mixtures of the invention to more than 95 wt .-%, in particular more than 98 wt .-% of the Mixture of at least two azo metal complexes.

The Azometallkomplexe can in the crystal solvent contain. Preferably contains the crystal per molecule Azometallkomplex no more than two molecules of solvent, particularly preferred not more than one molecule Solvent. Such solvents can its water, alcohols such as methanol, ethanol, propanol, diacetone alcohol or 2,2,3,3-tetrafluoropropanol, ketones such as acetone or butanone, dipolar solvents such as acetonitrile or dimethylformamide or mixtures thereof.

The mixtures according to the invention come in particular as a powder or granules or as a solution a solids content of at least 2 wt .-% in the trade. Prefers is the granular form, in particular granules with average particle size of 50 microns to 10 mm, in particular 100 to 800 microns. Such granules can for example by spray drying getting produced. The granules are characterized in particular their dust poverty.

The mixtures according to the invention are characterized by a good solubility out. They are good in non-fluorinated and fluorinated alcohols soluble. Preference is given to fluorinated alcohols. Such alcohols are, for example those having 3 to 9 C atoms, preferably propanol, butanol, pentanol, Hexanol, diacetone alcohol, 2,2,3,3-tetrafluoropropanol, octafluoropentanol or mixtures of these alcohols such. Propanol / diacetone alcohol, Butanol / diacetone alcohol, butanol / hexanol, butanol / nonanol. preferred mixing ratios for the listed Mixtures are for example 80:20 to 99: 1, preferably 90:10 to 98: 2nd

Also preferred are the solutions containing at least one organic solvent and at least 1 wt .-%, preferably at least 2 wt .-%, particularly preferably at least 5% by weight, in each case based on the solution, of the mixture according to the invention. As a preferred solvent is 2,2,3,3-tetrafluoropropanol, propanol, butanol, pentanol, Hexanol, diacetone alcohol, dibutyl ether or heptanone or mixtures used of it. Particularly preferred is 2,2,3,3-tetrafluoropropanol. Also particularly preferred is butanol. Also particularly preferred is butanol / diacetone alcohol in the mixing ratio 90:10 to 98: 2.

Prefers contain the solutions of the invention in addition the solvent only the mixtures according to the invention consisting of more than 95% by weight, in particular more than 98% by weight from the two Azometallkomplexen 1 and 2.

The The invention further relates to the use of the mixtures according to the invention from at least two azo metal complexes as light-absorbing compounds in the information layer of write-once optical data carriers.

Prefers In this use, the optical data carrier with red laser light, in particular with a wavelength described and read in the range of 600-700 nm, particularly preferred in the range of 625-660 nm.

The The invention further relates to an optical data carrier containing a preferably transparent, possibly already with one or a plurality of reflective layers coated substrate, on the surface of a light writable information layer, optionally one or more reflective layers and optionally a protective layer or a further substrate or a cover layer are applied, the one with red light, preferably with a wavelength in the range from 600-700 nm, preferably from 620 to 680 nm, especially preferably from 625 to 660 nm, preferably laser light, described and can be read, wherein the information layer is a light-absorbing Compound and optionally contains a binder, characterized in that the mixture according to the invention is used as the light-absorbing compound is used.

Prefers is an optical disk, containing a preferably transparent substrate, on the surface of which light writable information layer, one or more reflective layers and a protective layer or another substrate or a cover layer are applied, which with red light, preferably with a wavelength in the range from 600-700 nm, preferably from 620 to 680 nm, especially preferably from 625 to 660 nm, preferably laser light and can be read, wherein the information layer is a light-absorbing Compound and optionally contains a binder, characterized in that the mixture according to the invention is used as the light-absorbing compound is used.

The The light-absorbing compound should preferably be thermally changeable be. Preferably, the thermal change takes place at a temperature <600 ° C, especially preferably at a temperature <400 ° C, especially preferably at a temperature <300 ° C, in particular> 200 ° C. Such a change For example, a decomposition or chemical change of the chromophore center of the light-absorbing compound.

The preferred embodiment the light-absorbing compounds in the optical according to the invention Data storage correspond to the preferred embodiments of the mixture of Azometallkomplexen. In particular, it is a mixture containing a complex 1 of the formula (Ia) with a ligand of the formulas (XI) to (XIII), more particularly of the formulas (XIa) to (XId), and as Complex 2 has one of the formula (Ia) with one ligand of the formulas (XII) to (XV), more particularly of the formulas (XIVa) to (XIVd) and (XVa) to (XVI). Preferably contains the information layer as a light absorbing compound only one inventive mixture consisting of more than 95% by weight, in particular more than 98% by weight from the two Azometallkomplexen 1 and 2.

The light-absorbing compounds used according to the invention guarantee a sufficiently high reflectivity (preferably> 10%, in particular> 20%, very particularly> 40%) of the optical data carrier in the unrecorded state and a sufficiently high absorption for thermal degradation of the information layer in the case of selective illumination with focused light, when the wavelength of light is in the range of 600 to 700 nm. The contrast between written and unwritten locations on the data carrier is due to the change in reflectivity of the amplitude as well as the phase of the incident light realized after thermal degradation changed optical properties of the information layer.

The used according to the invention Light-absorbing compounds guarantee high light resistance the blank optical disk and the inscribed on the disk Information opposite Daylight, sunlight or under increased artificial irradiation for imitation of daylight.

The used according to the invention Light-absorbing compounds guarantee high sensitivity of the optical data carrier across from red laser light sufficient energy, so that the disk with high speed (≥ 2x, ≥ 4x, ≥ 8x) can be.

The preferred according to the invention used light-absorbing compounds are stable enough, so that the disk made with them the required climatic test Fulfills.

The mixtures according to the invention Azometallkomplexen are preferably on the optical disk applied by spin coats. As a rule, they are used alone. It can however, such mixtures according to the invention with each other or with other dyes with similar spectral Properties are mixed. The information layer can be next to the light-absorbing compound contains additives such as binders, Wetting agents, stabilizers, thinners and sensitizers and other ingredients. Preferably, the information layer contains no such additives. For spin-coats are preferably the listed above used solutions according to the invention.

Of the according to the invention optical Data storage can be next to the information layer more layers such as metal layers, dielectric layers and protective layers wear. Metals and dielectric layers serve u. a. for adjustment the reflectivity and the heat balance. Metals can depending on the laser wavelength Gold, silver, aluminum, alloys of these metals u. a. be. Dielectric layers are, for example, silicon dioxide and silicon nitride. Protective layers are, for example, photocurable, lacquers, (pressure-sensitive) Adhesive layers and protective films.

pressure Sensitive Adhesive layers mainly exist from acrylic adhesives. Nitto Denko DA-8320 or DA-8310, disclosed in JP-A 11-273147, may, for example For this Purpose to be used.

Protectors are preferably made of translucent material, preferably Plastic films. Suitable materials are, for example, polycarbonate, Copolycarbonates, PMMA and cyclic polyolefins. The thickness is for example 5 to 200 μm, preferably 10 to 180 μm, particularly preferably 20 to 150 μm, completely more preferably 50 to 120 microns.

Photohardenable paint are for example UV-curable Paints. These are, for example, acrylates and methacrylates, as disclosed, for example, in P.K. Oldring (Ed.), Chemistry & Technology of UV & EB formulations for Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London, pp. 31-235 are known. The Thickness is for example 5 to 200 μm, preferably 10 to 180 μm, particularly preferably 20 to 150 μm, completely more preferably 50 to 120 microns.

Of the optical media includes about it In addition, preferably at least one substrate. The substrate material is preferably transparent. Its thickness is preferably 0.3 mm, or more preferably at least 0.6 mm. Suitable substrate materials are preferably transparent thermoplastics or thermosets. suitable Thermoplastics are, for example, polycarbonate, copolycarbonates, PMMA and cyclic polyolefins.

The optical data carrier has, for example, the following layer structure (cf. 1 ): a preferably transparent substrate ( 11 ), an information layer ( 12 ), optionally a reflection layer ( 13 ), optionally an adhesive layer ( 14 ), another preferably transparent substrate ( 15 ).

The optical data carrier preferably contains an information layer ( 12 ).

Also preferably, the optical data carrier contains a reflection layer ( 13 ).

Likewise preferably, the optical data carrier contains a second substrate ( 15 ).

Also preferably, the optical data carrier contains a substrate ( 11 ) respectively. ( 15 ) made of polycarbonate or copolycarbonate.

Also preferably, the substrate ( 11 ) and ( 15 ) has a thickness of 0.3 to 1.5 mm, preferably 0.5 to 1.2 mm, in particular 0.6 mm.

Also particularly preferably, the structure of the optical data carrier is as follows:
a transparent substrate ( 11 ), an information layer which can be written on and read with light, preferably laser light ( 12 ), a reflection layer ( 13 ), an adhesive layer ( 14 ), another transparent substrate ( 15 ).

• – ein vorzugsweise transparentes Substrat (11), eine Informationsschicht (12), gegebenenfalls eine Reflexionsschicht (13), gegebenenfalls eine Kleberschicht (14), gegebenenfalls eine Schutz- oder dielektrische Schicht, gegebenenfalls eine Kleberschicht (14), gegebenenfalls eine Reflexionsschicht (13), eine Informationsschicht (12), ein weiteres vorzugsweise transparentes Substrat (15).
• – ein vorzugsweise transparentes Substrat (11), eine Informationsschicht (12), gegebenenfalls eine Reflexionsschicht (13), gegebenenfalls eine Kleberschicht (14), gegebenenfalls eine Schutz- oder dielektrische Schicht, eine Informationsschicht (12), gegebenenfalls eine Reflexionsschicht (13), ein weiteres vorzugsweise transparentes Substrat (15).
• – ein vorzugsweise transparentes Substrat (11), eine Informationsschicht (12), gegebenenfalls eine Reflexionsschicht (13), gegebenenfalls eine Schutz- oder dielektrische Schicht, eine Informationsschicht (12), gegebenenfalls eine Reflexionsschicht (13), gegebenenfalls eine Kleberschicht (14), ein weiteres vorzugsweise transparentes Substrat (15).

Likewise provided by the invention are optical data carriers which contain two information layers. They can be structured, for example, as follows:

• A preferably transparent substrate ( 11 ), an information layer ( 12 ), optionally a reflection layer ( 13 ), optionally an adhesive layer ( 14 ), optionally a protective or dielectric layer, optionally an adhesive layer ( 14 ), optionally a reflection layer ( 13 ), an information layer ( 12 ), another preferably transparent substrate ( 15 ).
• A preferably transparent substrate ( 11 ), an information layer ( 12 ), optionally a reflection layer ( 13 ), optionally an adhesive layer ( 14 ), optionally a protective or dielectric layer, an information layer ( 12 ), optionally a reflection layer ( 13 ), another preferably transparent substrate ( 15 ).
• A preferably transparent substrate ( 11 ), an information layer ( 12 ), optionally a reflection layer ( 13 ), optionally a protective or dielectric layer, an information layer ( 12 ), optionally a reflection layer ( 13 ), optionally an adhesive layer ( 14 ), another preferably transparent substrate ( 15 ).

Preferably contain these optical media with two information layers at least one reflection layer and at least one adhesive layer.

The The invention further relates to red light, preferably to light the wavelength 600-700 nm, in particular 620-660 nm, preferably 625 to 660 nm, in particular Laser light described optical disk according to the invention.

The The following examples illustrate the subject matter of the invention.

Examples

example 1

• a) 41.0 g of N, N-diethyl-m-phenylenediamine were dissolved in 350 ml of 1,2-dichloroethane under nitrogen atmosphere. 35.9 g of N, N-dimethylamidosulfonyl chloride were added, with the temperature rising to 38 ° C. After stirring at room temperature for 3 h, 27.7 g of triethylamine and 10.0 g of dimethylamidosulfonyl chloride were added. After stirring overnight at room temperature was discharged in 1000 ml of water and washed with 20 wt. Sodium hydroxide solution adjusted to pH = 7.5. The organic phase was separated, washed with 100 ml of water, dried over sodium sulfate and concentrated by rotary evaporation. The resulting oil was extracted three times with 100 ml of methylcyclohexane. Finally, 47.1 g (61% of theory) of a beige powder of the formula remained
  
  back.
• b) 2.45 g of 2-amino-4,5-dicyano-imidazole were dissolved in a mixture of 40 ml of water and 40 ml of 35 wt. Hydrochloric acid suspended. During 1.5 h, a sodium nitrite solution prepared from 1.3 g NaNO ₂ in 10 ml water was added dropwise at 0-5 ° C. 1 h, the suspension was stirred at 0-5 ° C under a considerable excess of nitrite.
• c) 5.0 g of the aniline derivative from a), 0.6 g of urea and 10.3 g of sodium acetate were initially charged in 100 ml of methanol. At 0-5 ° C, the diazotization prepared under b) was added during 1 h. Overnight allowed to come to room temperature with stirring. It was then filtered off with suction and dried at 60 ° C in a vacuum. This gave 6.7 g (88% of theory) of the azo dye of the formula
  
  as a red powder of melting point 156-157 ° C. λ _max = 493 nm (methanol) ε = 38263 l / mol cm.
• d) To a suspension of 3.6 g of the azo dye from c) in 50 ml of methanol were added 1.37 g of dimethyl sulfate and after 1 h 1.5 g of potassium carbonate at 30 ° C. After stirring at room temperature for 2 h, 1.0 g of dimethyl sulfate and, after 1 h, 1.1 g of potassium carbonate were added again. After a further 4 h stirring was filtered off, washed with 2x 5 ml of methanol and 100 ml of water and dried at 60 ° C in a vacuum. This gave 2.95 g (79% of theory) of a red powder of the formula
  
  from mp. 246-247 ° C. λ _max = 515 nm (methylene chloride) ε = 55127 l / mol cm.
• e) 1.0 g of the dye from d) were suspended in 25 ml of methanol at room temperature. 0.3 g of nickel acetate tetrahydrate was added. The mixture was stirred overnight at room temperature, filtered off with suction and dried at 50 ° C. under reduced pressure. 0.9 g (86% of theory) of a green-shining red-violet powder of the formula (IIIa)
  
  Mp> 280 ° C. λ _max = 541 nm (methylene chloride) ε = 107238 l / mol cm Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol) glassy film

Example 2

vom Schmp. 260-265°C (Zers.) erhalten.
λ_max = 553 nm (Methylenchlorid)
ε = 93649 l/mol cm
Löslichkeit: > 2 % in TFP (2,2,3,3-Tetrafluorpropanol)
glasartiger Film Using 3-phenyl-5-amino-1,2-4-thiadiazole, the azo metal complex of the formula (LIIIa)

of the mp 260-265 ° C (Zers.) received.
λ _max = 553 nm (methylene chloride)
ε = 93649 l / mol cm
Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)
glassy film

Example 3

vom Schmp. 246°C erhalten.
λ_max = 554 nm (Methylenchlorid)
ε = 84092 l/mol cm
Löslichkeit: > 2 % in TFP (2,2,3,3-Tetrafluorpropanol)
glasartiger FilmUsing 3-phenyl-5-amino-1,2-4-thiadiazole, the azo metal complex of the formula (LVa)

of the mp. 246 ° C received.
λ _max = 554 nm (methylene chloride)
ε = 84092 l / mol cm
Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)
glassy film

Example 4

• a) To a solution of 18.4 g of N, N-diethyl-m-phenylenediamine in 100 ml of 1,2-dichloroethane, a solution of 25.2 g of pyridine-3-sulfonyl chloride (Biorg. Med. Chem. Lett 2002, 12, 2097, J. Prakt. Chem. 1967, 36, 160) in 100 ml of 1,2-dichloroethane was added dropwise during 30 min, the temperature rising to 40 ° C. After stirring overnight at room temperature was discharged to 1 liter of water, with 20 percent strength. sodium hydroxide solution to pH = 7, the organic phase separated, shaken out with 100 ml of water, dried over sodium sulfate and concentrated by rotary evaporation. The residue was stirred twice with 100 ml of methylcyclohexane, finally filtered off with suction and dried at room temperature in vacuo. This gave 32.7 g (96% of theory) of the sulfonamide of the formula
  
  as a gray powder.
• b) 2.8 g of 2-amino-5-methyl-1,3,4-thiadiazole were dissolved in 32 ml of glacial acetic acid and 15 ml of formic acid solved. After cooling to 0-5 ° C were during 1.5 hours 7.8 g 40 wt. nitrosylsulfuric entered. 1 h was at 0-5 ° C touched.
• c) 7.5 g of the sulfonamide from a) were dissolved in 200 ml of methanol together with 1.5 g of urea and cooled to 5 ° C. The orange solution from b) was slowly added at a maximum of 10 ° C for 30 min, the pH with 20 percent strength. Sodium hydroxide was kept at a maximum of 1.5. The mixture was allowed to come to room temperature over 1 h and adjusted to pH = 3.5. It was filtered off with suction and washed with 100 ml of water. The moist filter cake was dried at 50 ° V in vacuo. 5.28 g (51% of theory) of a red powder of the formula were obtained
  
  λ _max = 503 nm (in methylene chloride) ε = 40557 l / mol cm.
• d) 2.0 g of the dye from c) were dissolved in 20 ml of N-methylpyrrolidone. 0.6 g of nickel acetate tetrahydrate was added. After stirring overnight at room temperature, 50 ml of water was added. It was filtered off, washed with 3x 10 ml of water and dried at 50 ° C in a vacuum. The red powder was stirred in 20 ml of toluene overnight, filtered off and dried at 50 ° C in a vacuum. 1.15 g (50% of theory) of a red powder of the formula (LIVa) were obtained.
  
  of the mp.> 260 ° C. λ _max = 554, 588 nm (methylene chloride) ε = 84622 l / mol cm (at 554 nm) Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol) gives a vitreous film

Example 5

• a) Analogously to Example 1 and Example 4, the azo dyes of the formula
  
  produced.
• b) 0.63 g of the dye from a) were mixed in 15 ml of acetonitrile with 0.4 ml of dimethyl sulfate and stirred at 40 ° C for 8 h. It was discharged to 50 ml of water and precipitated by the addition of sodium perchlorate. After filtering off with suction, washing with water and drying at 50 ° C. under reduced pressure, 0.48 g (59% of theory) of a red powder of the formula ## STR16 ## were obtained
  
• c) 0.3 g of the cationic dye from b) were mixed in 10 ml of methanol with 0.06 g of nickel acetate tetrahydrate and stirred overnight at room temperature. It was filtered off, washed with water and dried at 50 ° C in a vacuum. This gave 0.3 g (95% of theory) of a red powder of the formula
  
  of the mp.> 280 ° C. λ _max = 542, 578 nm (dimethylformamide) ε = 105444 l / mol cm (at 578 nm) Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

Example 6

It became a solution at room temperature the concentration of 20 g / l of a dye mixture in 2,2,3,3-tetrafluoropropanol produced. The dye mixture consisted of three parts by weight of the azo metal complex of the formula (IIIa) of Example 1 and two Mass fractions of the azo metal complex of the formula (LIVa) of the example 4. This solution was spin coated onto a pregrooved polycarbonate substrate applied. The pregrooved polycarbonate substrate was injection molded produced as a disk. The dimensions of the disk and the groove structure corresponded to those who usually for DVD + R be used. The disc with the dye layer as information carrier was steamed with 100 nm silver. It was then treated with UV-curable Acrylic varnish a second disk glued to the silver layer of the first. The thus finished disc was made by means of a commercial burner Plextor PX-708US burned at 4x speed. The written Data on the disk was recorded using a reference drive (Datarius CS4) analyzed. The modulation of the 14T pit was 66% and the bottom jitter was 6.91%.

Analogous results were obtained with the mixtures of the azo metal complex of the formula (IIIa) with one of the azo metal complexes of the formula (IIIa) or (LVa). Analogous results were also achieved when the mixing ratios c ₁ / c ₂ were varied within the limits 1 to 5. The discs can be written with at least 4x (4x) to at least 8x (8x) write speed.

Tabelle 2 (Azometallkomplexe 2)

Analogous results are also achieved when an azometallic complex of Table 1 is mixed with an azometallic complex of Table 2. Table 1 (Azometal Complexes 1)

Table 2 (azo metal complexes 2)

Claims (17)

Mixtures containing at least two different azo metal complexes, the ligands of the formula

wherein X ^{1 is} S or NH, X ² and X ^{3 are} independently CH or N, where the X ¹ -containing heterocycle may be substituted by nonionic radicals, R ^{0 is} NR ² R ^{2 '} , R ⁸ or K ⁺ An ^- R ² and R ^{2 'are} independently of one another optionally substituted by hydroxy, cyano or fluorine-substituted C ₁ -C ₆ alkyl and R ^{2 may} additionally be hydrogen, R ³ and R ^{4 are} independently of one another optionally substituted by hydroxy, cyano , Chlorine, acetoxy or -COOR ⁷ substituted C ₁ -C ₄ -alkyl or NR ³ R ^{4 is} optionally substituted pyrrolidino, piperidino, morpholino, piperazino or N-methyl-piperazino, R ⁵ and R ^{6 are} hydrogen or R ³ ; R ⁵ and R ⁴ ; R ⁶ independently of one another are together a - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -bridge, R ^{8 is} optionally substituted by chlorine, C ₁ -C ₄ -alkoxy, in particular methoxy, cyano, nitro or aceto-2 -, 3- or 4-pyridyl, pyridine-N-oxide-2-, 3- or 4-yl, pyrimidin-2 or 4-yl, benzothiazol-2 or -6-yl, K ⁺ for one optionally substituted by chlorine, C ₁ -C ₄ alkoxy, in particular methoxy, cyano, nitro or aceto-amino-substituted radical of the formula

R ^{11 is} C ₁ -C ₄ -alkyl, in particular methyl, ethyl or benzyl and An ^{- is} an anion. Mixture according to claim 1 corresponding to at least one azometallic complex carrying at least one ligand of formula (I) wherein X ^{1 is} NH and at least one different azometallic complex carrying at least one ligand of formula (I) wherein X ^{1 is} S and the remaining radicals have the meanings according to claim 1. Mixtures according to at least one of claims 1 or 2, comprising at least one azo metal complex containing at least one ligand of the formula (IIIa)

and at least one different azometallic complex containing at least one ligand of formula (IIIb)

wherein the radicals have the meanings described in claim 1 or 2. A mixture according to at least one of claims 1 to 3, containing at least one azo metal complex having at least one ligand of formula (XI), (XII) and / or (XIII)

and at least one different azometallic complex of the at least one ligand of the formula (XIV) and / or (XV)

wherein R ^{0 is} NR ² R ^{2 '} , R ⁸ or a radical of the formula

R ^{1 is} methyl or benzyl, R ² and R ^{2 '} independently of one another are methyl, ethyl or 2,2,2-trifluoroethyl and R ^{2 may} additionally be hydrogen, R ³ and R ⁴ are each independently methyl, Ethyl or NR ³ R ^{4 is} pyrrolidino, piperidino, morpholino, piperazino or N-methyl-piperazino, R ⁵ and R ^{6 are} hydrogen or R ³ ; R ⁵ and R ⁴ ; R ⁶ are each, independently of one another, CH ₂ ) ₂ - or - (CH ₂ ) ₃ - bridge, R ^{7 is} methyl or ethyl, R ^{8 is} 2-, 3- or 4-pyridyl and R ^{9 is} hydrogen, methyl, chlorine or bromine, R ^{10 is} trifluoromethyl, R ^{11 is} methyl, ethyl or benzyl and An ^{- is} an anion, wherein the radicals in ligands (XI) to (XV) need not have the same meaning. Mixture according to at least one of Claims 1 to 4, characterized in that it comprises at least one azo metal complex of the formula (Ia)

in which the two ligands I independently of one another have the meaning given in claims 1 to 4 and M is a metal. Mixture according to at least one of claims 1 to 5, characterized in that as metal of the Azometallkomplexes a divalent transition metal, in particular Cu, Ni, Co, Zn, Pd, preferably Cu, Ni and Co, particularly preferably Ni is used. Mixture according to at least one of claims 4, characterized in that they contain ligands of the formulas (XI), (XIV) and (XV), wherein R ^{0 is} NR ² R ^{2 '} , R ⁸ or a radical of the formula

R ^{1 is} methyl, R ^{2 is} methyl or 2,2,2-trifluoroethyl, R ^{2 'is} hydrogen or methyl, R ³ and R ^{4 are} ethyl and R ⁵ and R ^{6 is} hydrogen or NR ³ R ⁴ for pyrrolidino and R ⁵ and R ⁶ for hydrogen or R ³ , R ⁵ for a -CH ₂ -CH ₂ -bridge and R ⁴ for methyl or ethyl and R ⁶ for hydrogen or R ³ ; R ⁵ and R ⁴ ; R ^{6 is} a -CH ₂ -CH ₂ -CH ₂ -bridge, R ^{8 is} 2- or 3-pyridyl, R ^{9 is} hydrogen, methyl or bromine, R ^{11 is} methyl and An ^{- is} an anion. Mixtures according to at least one of claims 5 to 7, characterized in that they contain nickel complexes of the formula (Ia) with the following ligands:

wherein R ^{0 is} one of the following formulas:

where An ^{- stands} for an anion. Use of mixtures according to at least one of claims 1 to 8 as a light absorbing compound in the information layer of write-once optical data media. Use according to claim 9, characterized the optical disk with red laser light, in particular with a wavelength in the range 600-700 nm can be written and read. solution mixtures according to claim 1, characterized in that it at least 1 wt .-% of the mixture according to claim 1 contains and that as a solvent 2,2,3,3-tetrafluoropropanol, propanol, butanol, pentanol, hexanol, Diacetone alcohol, dibutyl ether, heptanone or mixtures thereof used becomes. solution mixtures of azo metal complexes according to claim 11, characterized in that as a solvent 2,2,3,3-tetrafluoropropanol is used. Optical data carrier containing a preferably transparent possibly already with one or more reflection layers coated substrate having on its surface a light writable information layer, optionally one or more reflective layers and optionally a protective layer or another substrate or a cover layer are applied, which with red light, preferably laser light, can be described and read, with the information layer a light absorbing compound and optionally a binder contains characterized in that at least as light-absorbing compound a mixture of two azo metal complexes after at least one of claims 1 to 8 is used. Optical data carrier according to claim 13 containing a preferably transparent substrate, on the surface of a light writable information layer, a reflective layer, an adhesive layer and a further substrate are applied, the with red light, preferably laser light, described and read can be, wherein the information layer is a light-absorbing Contains compound characterized in that a light-absorbing compound Mixture of two azo metal complexes according to at least one of claims 1 to 8 is used. Optical data carrier according to at least one of claims 13 or 14, characterized in that as light-absorbing compound a mixture according to claim 4 is used. Method for producing the optical data carriers according to at least one of the claims 13 to 15, which is characterized in that one is preferably transparent substrate with a mixture according to claim 1 optionally in combination with suitable binders and additives and, if appropriate, suitable solvents coated and optionally with a reflective layer, a Adhesive layer and another substrate provides. With red light, in particular red laser light, described optical disk according to at least one of the claims 13 to 15.