WO2006007983A1

WO2006007983A1 - Mixtures of azo metal complexes as light-absorbing compounds in the information layer of optical data carriers

Info

Publication number: WO2006007983A1
Application number: PCT/EP2005/007352
Authority: WO
Inventors: Horst Berneth; Karin HASSENRÜCK; Timo Meyer-Friedrichsen; Josef-Walter Stawitz; Ulrich Feldhues; Friedrich-Karl Bruder; Rafael Oser
Original assignee: Lanxess Deutschland Gmbh
Priority date: 2004-07-19
Filing date: 2005-07-07
Publication date: 2006-01-26
Also published as: TW200615941A; DE102004034866A1

Abstract

The invention relates to mixtures containing at least two different azo metal complexes which contain ligands of formula (I), wherein the substituents have the meaning cited in claim 1.

Description

MIXTURES OF AZOMETAL COMPLEXES AS

LIGHT ABSORBENT COMPOUNDS IN THE

INFORMATION LAYER OF OPTICAL DATA CARRIES

The invention relates to mixtures of azo metal complexes, specific azo metal complexes, a process for their preparation, the azo compounds which function as ligands of the metal complexes and their preparation, which are based on the azo compounds

Coupling components and their preparation and optical data storage containing the metal complexes in their Iαformationsschicht, as well as the application of the above dyes to a polymer substrate, in particular polycarbonate, by spin coating or vapor deposition.

The write-once optical data carriers using special light-absorbing substances or mixtures thereof are particularly suitable for use in high-density recordable optical data storage devices which operate with blue laser diodes, in particular GaN or SHG laser diodes (360-460 nm) and / or for the For use with DVD-R or CD-R discs that use red (635 - 660 nm) or infrared (780 - 830 nm) laser diodes

The recordable compact disc (CD-R, 780 nm) has recently undergone enormous volume growth and represents the technically established system.

Currently, the next generation of optical data storage - the DVD - is introduced to the market. By using shorter wavelength laser radiation (635 to 660 nm) and higher numerical aperture NA, the storage density can be increased. The recordable

Format is in this case the DVD-R.

Today, optical data storage formats using blue laser diodes (GaN base, JP 08191171 or Second Harmony generation SHG JP 09050629) (360 nm to 460 nm) with high laser power are being developed. 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 on the basis of semiconductor laser diodes, 390 nm _r.

In the patent literature are described on dye-based writable optical Daten¬ memory, which are equally suitable for CD-R and DVD-R systems (JP-A 11 043 481 and JP-A 10 181 206). In this case, use is made of the fact that the IR wavelength 780 nm of the CDR lies at the foot of the long-wavelength edge of the absorption peak of the dye, the red one for a high reflectivity and a high modulation depth of the read-out signal, and for sufficient sensitivity during writing Wavelength 635 nm or 650 nm of the DVD-R at the foot of the short-wave edge of the

Absorption peaks of the dye is. This concept is described 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 Pat. No. 5,266,699 in the range 450 nm Working wavelength on the short-wave edge and the red and IR range on the long-wave edge of the absorption peak extended.

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

Crystallization of the light-absorbing substances is prevented.

The amorphous layer of light-absorbing substances should preferably have a high heat resistance, otherwise other layers of organic or inorganic material, which are applied by sputtering or vapor deposition on the light-absorbing information layer via diffusion form blurred boundary surfaces and thus affect the reflectivity unfavorable. In addition, a light-absorbing substance with too low heat resistance at the interface to a polymer carrier can diffuse in these and in turn affect the reflectivity unfavorable.

Too high a vapor pressure of a light-absorbing substance can sublime in the above-mentioned sputtering or vapor deposition of further layers in a high vacuum and thus reduce the desired layer thickness. This in turn leads to a negative influence on the reflectivity.

JP 11-310 728 describes an optical recording medium containing certain nonionic azo metal complexes in its information layer. These azo metal complexes contain azo dyes that must contain at least 2 fluorine atoms. The

Azo dyes further contain a grouping of the formula -NH-SO ₂ -Y, wherein Y is an alkyl or aryl radical. The optical data memory is suitable for a write and read laser wavelength of 630-660 nm. The object of the invention is therefore to provide suitable compounds which meet 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 data carrier, in particular for high density recordable optical data storage formats in a Laserwellen¬ length range from 340 to 680 nm meet.

Surprisingly, it has been found that, as light-absorbing compounds, mixtures of azo metal complexes can fulfill the abovementioned requirement profile particularly well.

The invention therefore relates to mixtures containing at least two different

Azometal complexes, the ligands of the formula (I)

wherein χi is S or NH,

X 1 and X 1 independently of one another are CH or N,

where the heterocycle containing X 1 can 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 each other optionally substituted by hydroxy, cyano or fluorine-substituted Ci-C _δ- alkyl and

R ^{2 can} additionally be hydrogen,

R ³ and R ^{4 are} independently of each other optionally substituted by hydroxy, cyano, chlorine, acetoxy or -COOR ⁷ substituted Ci-C ₄ alkyl or

NR ³ R ^{4 represents} optionally substituted pyrrolidino, piperidino, morpholino,

Piperazino or N-methyl-piperaziho stands ,. R ⁵ vmd R ^{6 are} hydrogen or

R, R and R? 4; .uR6 independently of one another are together a - (CH ₂ ^ - or - (CH ₂ ) 3 bridge,

R ^{8 is} optionally substituted by chlorine, C 1 -C 4 -alkoxy, in particular methoxy,

Cyano, nitro or acetamino substituted 2- or 3-thienyl, 2-, 3- or 4-pyridyl, pyridine-N-oxide-2-, 3- or 4-yl, pyrimidine-2 or 4-yl, benzothiazole Stands for -2- or -6-yl,

K ^{+ is} an optionally substituted by chlorine, C ^ -C ^ alkoxy, in particular

Methoxy, cyano, nitro or acetamino 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,

contain.

Preferred substituents of the heterocycle containing X 1 are preferably trifluoromethyl, cyano, nitro, -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} Ci-C4-alkyl, in particular methyl or ethyl.

Preference is given to mixtures according to the invention comprising at least one azo metal complex which carries at least one ligand of the formula (I) in which

χl is NH and at least one different azometallic complex, which carries at least one ligand of the formula (T), wherein χl is S and the remaining radicals have the above meanings.

Particular preference is given to mixtures comprising at least one azo metal complex which comprises at least one ligand of the formula (IIa)

and at least one different azometallic complex, the at least one

Ligands of the formula (IHb) contains

wherein the radicals have the meanings described above.

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

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

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 (XHI)

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

possesses, in which

R ^{0 is} NR ² R ² , R ⁸ or 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 represents} pyrrolidino, piperidino, morpholino, piperazino or N-methylpiperazino,

R ⁵ and R ^{6 are} hydrogen or

R ³ , R ⁵ and R ⁴ , R ⁶ independently of one another are together a - (CK ₂ ) I or - (CH ₂ V bridge,

R ^{7 is} methyl or ethyl,

R ^{8 is} 2-thienyl, pyridine-N-oxide-3-yl, 2-, 3- or 4-pyridyl,

R ^{9 is} hydrogen, methyl, trifluoromethyl, chlorine or bromine,

R ^! 10 is trifluoromethyl,

R 11 is methyl, ethyl or benzyl,

R ^{12 is} hydrogen, cyano or nitro and

An ^{¬ stands} for an anion,

where the radicals in ligands (XI) to (XV) need not have the same meaning.

With formula (XU) is also here and further down, z. In formula (Eb), also the isomer of the formula

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

With formula (XIH) are here and further down, z. Example in formula (Tic), and the isomers of the formulas

and

and the mixture of 2 or 3 of these isomers of formulas (XIH), (XHIa) and (Xmb).

In a preferred embodiment, the azo metal complexes are present as 1: 1 or 1: 2 metal: azo complexes, more preferably as 1: 2 metal: azo complexes.

Clearly preferred are those Azometallkomplexe containing two identical or different, in particular two identical ligands of the formula (I). If it concerns two different ligands, then also the statistical mixtures of the complexes obtainable from ligands and metal are meant.

Preferred are those Azometallkomplexe, which are characterized in that they are the

Formula (Ia) [(D] 2+

M (Ia)

in which the two ligands (I) independently of one another have the abovementioned meaning of the ligands of the formulas (I), in particular (HIa), (DIb) or (XI) to (XVI), and

M stands for a metal.

Divalent transition metals, in particular Cu, Ni, Co, Zn, Pd, are suitable as preferred metals for the azo metal complexes. The metals Cu, Ni and Co. are preferred. Ni is particularly preferred.

Also preferred are those azometallic complexes which are characterized in that they correspond to the formula (Ib)

[ ⁽ »] ^" M ³⁺ An " ^(Ib)

in which the two ligands (I) independently of one another have the abovementioned meaning of the ligands of the formulas (I), in particular (DIa), (DIb) or (XI) to (XVI),

- M stands for a metal and

An ^"stands for an anion.

As preferred metals for the Azometallkomplexe come trivalent transition metals, in particular Co, Cr in question. Preferred is Co.

Particularly preferred are the azo metal complexes containing ligands of the formulas (DIa) or (JHb), in particular (XI), (XIV) and (XV).

The 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 ^{r 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-thienyl, 2- or 3-pyridyl,

R ^{9 is} hydrogen, methyl or bromine,

R ¹¹ for methyl and

An ^' for an anion.

In the formulas (XI), (XTV) and (XV) are particularly preferred

R ⁰ for MR 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 _r CH ₂ bridge and

R ^{9 is} methyl or bromine.

In the formulas (XI). (XTV) and (XV) are also particularly preferred R ^{0 is} 3-pyridyl,

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 (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.

Preferred mixtures of azo metal complexes are those which contain nickel complexes of the formula (Ia) with the following ligands:

(XId),

(XVd)

(XVh)

(XVI)

(XVId)

wherein

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

where An ^"stands for an anion.

Particular preference is given to the nickel complexes of the formula (Ia) which have two identical leaflets of the formula (I), which both correspond to the same of the abovementioned formulas (XIa) to (XVIh) and which also carry the same radical R ⁰ .

Likewise particularly preferred are the nickel complexes of the formula (Ia) which have two different ligands of the formula (I) ₅ but which both correspond to the same ones of the abovementioned formulas (XIa) to (XVIh), where R ⁰ for one of the ligands

T) stands and for the other ligand R ⁰ for

stands.

In particular, the latter are usually mixtures of metal complexes with

- 2 ligands, both R =

wear,

2 ligands, one of which R ⁰ =

and the other R ^u = carries.

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, there is are colorless anions. Suitable anions are for example chloride,

Bromide, iodide, nitrate, carbonate, bicarbonate, sulfate, hydrogen sulfate, azide, cyanate, thiocyanate, tetrafluoroborate, perchlorate, hexafluorosilicate, hexafluorophosphate, methosulfate, ethosulfate, C ₁ - to C ₁₀ alkane sulfonate, Ci to Ci ₀ -Perfluoralkansulfonat, ( CFsSC ^ N ^", optionally substituted by chlorine, hydroxy, Cr to C ₄ alkoxy-substituted Cr to C ₀ - alkanoate, oxalate, optionally substituted by nitro, cyano, hydroxy, C ₁ - to C ₂₅ -alkyl, perfluoro-

Ci to C ₄ -alkyl, Ci to C ₄ alkoxycarbonyl or chlorine-substituted benzene or naphthalene or biphenyl disulphonate, optionally substituted by nitro, cyano, hydroxy, Cr to C _4- alkyl, Ci to C ₄ alkoxy, Ci to C ₄ alkoxycarbonyl or chlorine-substituted benzene or naphthalene or Biphenyldisulfonat, optionally substituted by nitro, cyano, hydroxy, Ci to _C4 alkyl, Ci to C ₄ alkoxy, C ₁ - to C ₄ -alkoxycarbonyl , Benzoyl, chlorobenzoyl or

Toluoyl substituted benzoate, the anion of naphthalene or benzenedicarboxylic acid, Diphenyletherdisulfonat, mono-, di- or trinitrophenolate, tetraphenylborate, cyanotriphenylborate, tetra-Cr to C ₂ o-alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarba-nido -undecaborate (l-) or (2-) which are optionally substituted on the B and / or C atoms by one or two C 1 to C 10 alkyl or phenyl groups,

Dodecahydro-dicarbadodecaborate ^ -) or B-Ci to Cπ-alkyl-C-phenyl-dodecahydro dicarbadodecaborate (l-), polystyrene sulfonate, poly (meth) acrylate, polyallylsulfonate.

Preference is given to bromide, iodide, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, dodecylbenzenesulfonate, tetradecanesulfonate, polystyrenesulfonate.

Can continue as anions An ^"all monovalent anions or one equivalent of a polyvalent anion of a dye can be used. Preferably, the anionic dye ^to" an absorption spectrum similar to the cationic azo metal 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 ^" For example, from DE-A 101 36 064 known. 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.

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 (Ea) to (He) in which R ^{0 is} K ⁺ An ^' , where

An ^" for iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate or the anion or an 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 and R 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 ₂ ) ₂ -CH ₂ -CH (CH ₃ ) - or -O (CH ₂ ) ₂ - and

R ^{107 is} hydrogen or sulfo.

Suitable oxonol dyes are, for. B. those of the formula (CI)

wherein

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

Preferably, in formula (CI), B and C are the same.

Preferably, the ring B together with the two carbon atoms and the

Oxygen atom for a remainder of the formulas

where of the carbon atom marked with * the double bond to the rest of the formula

(CI) goes out,

and the ring C together with the two carbon atoms and the oxygen atom for a remainder 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,

R ¹¹⁶ and R ¹¹⁷ independently represent hydrogen, methyl, ethyl, propyl or together represent a - (CH ₂ ) ^ ₅ - (CH ₂ ) S-, - (CH ₂ ) 6 bridge.

Suitable metal complex dyes are, for. Eg those of the formula (CII)

wherein

Y and Y are independently -O- or -COO-,

M ^• 101 represents 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.

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 and R independently of one another represent hydrogen or methyl,

R ^] 113 is methyl or trifluoromethyl,

R 115 is phenyl, chlorophenyl or tolyl. M is preferably Ni, Co, Cr, Fe, Cu.

Suitable cyanine dyes are, for. B. those of the formula (CHI)

wherein

Y ^1U3 and Y ^lü4 independently of one another represent S, C (CH ₃ ) ₂ or -CH = CH-,

R ¹³¹ and R ^{132 are} independently of one another - (CH ₂ VCOO ^" , - (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.

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 * leads to the rest of the compound (CW),

stands,

Y ^{105 is} S, C (CH ₃ ) ₂ or -CH = CH-,

R ^{135 is} methyl, ethyl, benzyl, - <CH ₂ ) _n -COO ^" , - (CH ₂ VSO ₃ ^' or - (CH ₂ VO-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 VCOO-, - (CH ₂ VSO ₃ ^' or - (CH ₂ VO-SO ₃ - stand,

R ^{123 is} methyl or trifluoromethyl,

R ^{124 is} cyano, methoxycarbonyl or ethoxycarbonyl,

R ^{125 is} phenyl, chlorophenyl or tolyl,

R ¹²⁹ and R ¹³⁰ independently of one another represent hydrogen, methyl, ethyl, propyl or together represent a - (CH ₂ V, - (CH ₂ ) _S -, - (CH ₂ VBrücke stand and

n is an integer from 2 to 5, wherein at least one of R ¹³⁵ , R ¹²¹ and R ^{122 is} - (CH ₂ VCOO ^" , - (CH ₂ ) _H -SO ₃ - or - (CH ₂ ) _H -O-SO ₃ ^" , preferably Kr- (CH ₂ VSO ₃ ^" stands.

Also suitable merocyanine dyes are, for. B. those of formula (CV)

wherein

the ring G for a remainder of the formulas

(CV) goes out,

stands,

Y rl ¹ O ^U 6 ^{Ö stands} for O, S or -CH = CH-,

Y ^1U 'is N ₃ CH or C-CN,

R ^{1 is} hydrogen, methyl, ethyl, propyl or phenyl, R ^{127 is} hydrogen, methyl, ethyl, propyl, butyl, - (CH ₂ VCOO ^" , - (CH ₂ VSO ₃ - or - (CH ₂ VO-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 ) ₁ -COO ^" , - (CH ₂ VSO ₃ ^" or - (CH ₂ VO-SO ₃ ^") ,

R ^{123 is} methyl or trifluoromethyl,

R ^{124 is} cyano, methoxycarbonyl or ethoxycarbonyl,

R ^{125 is} phenyl, chlorophenyl or tolyl,

R ¹²⁹ and R ¹³⁰ independently of one another represent hydrogen, methyl, ethyl, propyl or together represent a - (CH ₂ V, - (CH ₂ V, - (CH ₂ ) ₆ - bridge and

n is an integer from 3 to 5,

wherein at least one of R ¹²⁷ , R ¹²¹ and R ^{122 is} - (CH ₂ VCOO ^" , - (CH ₂ VSO ₃ ^" or - (CH ₂ VO-SO ₃ ^" , preferably UOr- (CH ₂ VSO ₃ ^" .

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 _O -aryl,

R ¹⁴¹ and R ¹⁴² independently of one another represent hydrogen, C _r to C ₆ -alkyl, C ₅ - to C ₇ -

Cycloalkyl, C ₆ - to C ₁₀ -aryl or C ₇ - to cis-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 _O -aryl,

Y ^{10S is} furN or CR ¹ ^,

R ^{15S is} hydrogen or cyano,

for a rest of the formulas

(CVIc) stands,

wherein

X ^{1 '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 represent hydrogen, C ₁ - to C ₆ -AIk ^ l, C ₅ - to C ₇ - cycloalkyl, C ₆ - to Cio-aryl or C ₇ - to C ₁₅ aralkyl, or are

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 _χ io5_ _R i47 _{mr 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 independently represents d- to C ₆ alkyl, C ₃ - to C ₆ -alkenyl, C ₅ - to C ₇ -

Cycloalkyl or C ₇ - to C are ₆ aralkyl,

R ¹⁶⁰ and R ¹¹ 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 nonionic Radicals can be substituted,

R ¹⁵⁴ and R ¹⁵⁵ independently represent hydrogen, C ₁ - or to Cio-aryl or a heterocyclic radical - to C ₁₆ alkyl, C ₄ - to C ₇ - cycloalkyl, C ₇ - to C ₆ aralkyl, C ₆

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 _r 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 represents} 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 , 0-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 1-4 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 for -CCH ₂ ) _n -COCr, - (CH ₂ ) _H -SO ₃ ^" or - (CH ₂ VO-SO ₃ ^" , preferably for - (CH ₂ ) _n -SO ₃ ^" and stand 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.

Particularly preferred mixtures of azo metal complexes are those which comprise a nickel complex of the formula (Ia) having two identical ligands of the formulas (XIa) to (XId) and one nickel complexes of the formula (Ia) having two ligands of the formulas (XtVa) to

(XTVd) included.

Likewise particularly preferred mixtures of azo metal complexes are those which comprise a nickel complex of the formula (Ia) having two identical ligands of the formers (XIa) to (XId) and a nickel complexes of the formula (Ia) having two identical ligands of the formers (XVa) to (XVI ) contain.

Likewise particularly preferred mixtures of azo metal complexes are those which comprise a nickel complex of the formula (Ia) having two identical ligands of the formula (XIa) to (XId) and a nickel complex of the formula (Ia) having two identical ligands of the formulas (XVIa) to (XVHi Very particularly preferred mixtures of azo metal complexes are those which contain a nickel complex of the formula (Ia) having two identical ligands of the formula (XIa) and a nickel complexes of the formula (Ia) having two identical ligands of the formula (XTVa).

Likewise very particularly preferred mixtures of azo metal complexes are those which comprise a nickel complex of the formula (Ia) having two identical ligands of the formula (XIa) and a nickel complex of the formula (Ia) having two identical ligands of the formers (XVa),

(XVe), (XVi).

R ⁰ in these particularly and very particularly preferred mixtures of azo metal complexes is preferably one of the following formers:

where An ^"stands for an anion.

C 1 -C 5 -alkyl radicals are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, which may be substituted by the radicals added above can. Examples of such substituted alkyl radicals are: perfluorinated

Methyl, perfluorinated ethyl, 2,2-difluoroethyl, 3,3,3-trifluoroethyl, perfluorobutyl, cyanoethyl, methoxyethyl, chloroethyl, acetoxyethyl, methoxycarbonylethyl.

Likewise preferred are azo metal complexes with ligands of the formula (XI) to (XVI), the latter having no fluorine atoms.

The particularly preferred azo metal complexes of the formula (Ia) each have 2 ligands, as can be taken from the formers (XI) to (XVT). It is assumed that they are in the form of the formulas (Ha) to (Hf):

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 (Ha) to (IEf) characterize sub-formulas of (Ia).

Of course, the mixtures according to the invention may contain, in addition to the mixture of at least two azo metal complexes, further org. contain light-absorbing compounds ent. Preferably, the mixtures according to the invention consist of more than 95% by weight, in particular more than 98% by weight, of the mixture of the at least two azo metal complexes.

The azo metal complexes may contain solvents in the crystal. Preferably, the crystal does not contain more than two molecules of solvent per molecule of azometallic complex, more preferably not more than one molecule of solvent. Such solvents may be water, alcohols such as methanol, ethanol, propanol, diacetone alcohol or 2,2,3,3-Tetrafluorpropaαol, ketones such as acetone or butanone, dipolar solvents such as acetonitrile, N-methylpyrrolidone or dimethylformamide or mixtures thereof.

The mixtures according to the invention come in particular as powder or granules or as a solution having a solids content of at least 2 wt .-% in the trade. Preference is given to the granulate form, in particular granules having an average particle size of 50 μm to

10 mm, in particular 100 to 800 microns. Such granules can be prepared, for example, by spray drying. The granules are characterized in particular by their dust poverty.

The mixtures according to the invention are distinguished by good solubility. They are readily soluble in non-fluorinated and fluorinated alcohols. 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 else mixtures of these alcohols, such as e.g. 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: 2.

Also preferred are the solutions containing at least one organic solvent and at least 1 wt .-%, preferably at least 2 wt .-%, more preferably at least 5 wt .-%, each based on the solution of the inventive mixture. The preferred solvent is 2,2,3,3-tetrafluoropropanol, propanol, butanol,

Pentanol, hexanol, diacetone alcohol, dibutyl ether or heptanone or mixtures thereof. Particularly preferred is 2,2,3,3-tetrafluoropropanol. Also particularly preferred is butanol. Also particularly preferred is butanol / diacetone alcohol in a mixing ratio of 90:10 to 98: 2.

In addition to the solvent, the solutions according to the invention preferably contain only the mixtures according to the invention consisting of more than 95% by weight, in particular more than 98% by weight, of the two azo metal complexes 1 and 2.

The invention further relates to the use of the mixtures according to the invention of at least two azo metal complexes as light-absorbing compounds in the information layer of write-once optical data carriers. In this application, the optical data carrier is preferably written and read with red laser light, in particular with a wavelength in the range of 600-700 nm, particularly preferably in the range of 625-660 nm.

The invention further relates to an optical data carrier, comprising a preferably transparent, optionally already coated with one or more reflective layers substrate on the surface of a writable light 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 with a wavelength in the range of 600-700 nm, preferably from 620 to 680 nm, most preferably from 625 to 660 nm, preferably

Laser light, can be written and read, wherein the information layer contains a licht¬ absorbing compound and optionally a binder, characterized in that the mixture according to the invention is used as the light-absorbing compound.

Preference is given to an optical data carrier containing a preferably transparent substrate, on the surface of which a light-writable information layer, one or more reflection layers and a protective layer or another substrate or a cover layer are applied, which is coated with red light, preferably with a wavelength in the Range of 600-700 nm, preferably from 620 to 680 nm, most preferably from 625 to 660 nm, preferably laser light, can be described and read, the

Information layer contains a light-absorbing compound and optionally a binder, characterized in that as a light-absorbing compound erfindungs¬ proper mixture is used.

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

The preferred embodiment of the light-absorbing compounds in the optical data memory according to the invention correspond to the preferred embodiments of the mixture of azo metal complexes according to the invention. In particular, it is a mixture containing a complex 1 of the formula (Ia) with a ligand of Formulas (XI) to (XHI), more particularly of the formulas (XIa) to (XId), and as Complex 2 one of the formula (Ia) with a ligand of the formulas (XTV) to (XVT), especially of the formulas (XIVa ) to (XTVd), (XVa) to (XVl) and (XVIa) to (XVIh). Preferably, the Infoπnationsschicht contains as light-absorbing compound only a mixture according to the invention consisting of more than 95 wt .-%, in particular more than 98 wt .-% of 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 at point-specific

Focused light illumination 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 realized by the change in reflectivity of the amplitude as well as the phase of the incident light by the optical properties of the information layer which have changed after the thermal degradation.

The light-absorbing compounds used according to the invention guarantee a high light resistance of the unwritten optical data carrier as well as the information inscribed on the data carrier against daylight, sunlight or under increased artificial irradiation for imitation of daylight.

The light-absorbing compounds used according to the invention guarantee a high level of

Sensitivity of the optical disk against red laser light of sufficient energy, so that the disk at high speed (> 2x,> 4x,> 8x) can be described.

The light-absorbing compounds preferably used according to the invention are stable enough so that the disk produced with them fulfills the required climatic test.

The mixtures of azometaU complexes according to the invention are preferably applied to the optical data carrier by spin coats. As a rule, they are used alone. However, it is also possible for such mixtures according to the invention to be mixed with one another or else with other dyes having similar spectral properties. The information layer may contain, in addition to the light-absorbing compound, additives such as binders, wetting agents, stabilizers, thinners and sensitizers, as well as other ingredients. Preferably, the information layer does not contain such additives. To the Spin coats are preferably used the solutions according to the invention listed above.

The optical data storage device according to the invention can carry, in addition to the information layer, further layers such as metal layers, dielectric layers and protective layers. Metals and dielectric layers serve u. a. for adjusting the reflectivity and the

Heat balance. Metals may, depending on 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 consist mainly of acrylic adhesives. Nitto Denko DA-

For example, 8320 or DA-8310, disclosed in JP-A 11-273147, can be used for this purpose.

Protective films are preferably made of translucent material, preferably plastic films. Suitable materials include polycarbonate, copolycarbonates, PMMA and cyclic polyolefins. The thickness is, for example, 5 to 200 .mu.m, preferably 10 to 180 .mu.m, more preferably 20 to 150 .mu.m, most preferably 50 to 120 .mu.m.

Photo-curable lacquers are, for example, UV-curable lacquers. These are, for example, acrylates and methacrylates, as described, 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 .mu.m, preferably 10 to 180 .mu.m, more preferably 20 to 150 .mu.m, most preferably 50 to 120 .mu.m.

In addition, the optical data carrier preferably contains at least one substrate. The substrate material is preferably transparent. The 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 (see Fig. 1): a preferably transparent substrate (11), an information layer (12), optionally one

Reflection layer (13), optionally an adhesive layer (14), another preferably transparent substrate (15) :. The optical data carrier preferably contains an information layer (12).

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

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

Likewise preferably, the optical data carrier contains a substrate (11) or (15) 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 (12) which can be written on and read with light, preferably laser light, a reflection layer (13), an adhesive layer (14), a further transparent substrate (15).

Likewise provided by the invention are optical data carriers which contain two layers of information. 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 reflective layer (13), optionally an adhesive layer (14), another preferably transparent substrate (15). Preferably, these optical data carriers with two information frames contain at least one reflection layer and at least one adhesive layer.

The invention further relates to red light, preferably with light of wavelength 600-700 nm, in particular 620-660 nm, preferably 625 to 660 nm, in particular laser light described optical data carrier according to the invention.

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, the temperature rising to 38 ⁰ C. After stirring for 3 hours at room temperature, 27.7 g of triethylamine and 10.0 g of dimethylamidosulfonic acid chloride were added. After stirring overnight at room temperature was discharged in 1000 ml of water and washed with 20 wt. Sodium hydroxide adjusted to pH = 7.5 ge. 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. For 1.5 h was added dropwise at 0-5 ⁰ C a sodium nitrite solution was prepared from 1.3 g of NaNO ₂ in 10 ml of water thereto. 1 h, the suspension was stirred at 0-5 ⁰ 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 ⁰ C, the diazotization prepared under b) was added during 1 h. Overnight allowed to come to room temperature with stirring. Then it was filtered off and dried at 60 ⁰ C in a vacuum. One received

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 1 / mol cm.

To a suspension of 3.6 g of the azo dye from c) in 50 ml of methanol, 1.37 g of dimethyl sulfate and after 1 h, 1.5 g of potassium carbonate at 30 ⁰ C was added. 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 ⁰ C in vacuo. This gave 2.95 g (79% of theory) of a red powder of the formula

from mp. 246-247 ⁰ C.

λ _max = 515 nm (methylene chloride)

ε = 55127 1 / mol cm. 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)

M.p.> 280 ⁰ C

λ _max = 541 nm (methylene chloride)

ε = 107238 1 / mol cm

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

glassy film

Example 2

Using 3-phenyl-5-amino-1, 2-4-thiadiazole, the azo metal complex of the formula (LEIa)

of the m. 260-265 ⁰ C (Zers.) received.

λ _max = 553 nm (methylene chloride)

ε = 93649 1 / mol cm

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

glassy film

Example 3

Using 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 1 / 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 over 30 min, the temperature rising to 40 ° C. After stirring overnight at room temperature, was discharged to 1 1 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-ammo-5-methyl-l, 3,4-thiadiazole were dissolved in 32 ml of glacial acetic acid and 15 ml of formic acid. After cooling to 0-5 ⁰ C were 7.8 g 40 wt. Percent during 1.5 h. Nitrosylsulfuric acid registered. 1 h was stirred at 0-5 ⁰ C.

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 1O ⁰ 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 during 1 h and adjusted to pH = 3.5. It was sucked off and with

Washed 100 ml of water. The moist filter cake was dried at 50 ^° C. 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 1 / 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 ge and dried at 50 ⁰ C in vacuo. The red powder was stirred in 20 ml of toluene overnight, filtered off and dried at 50 ⁰ C in a vacuum. 1.15 g (50% of theory) of a red powder of the formula (LIVa) were obtained.

of the mp> 260 ⁰ C.

λ _max = 554, 588 nm (methylene chloride)

ε = 84622 1 / mol cm (at 554 nm)

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

gives a glassy 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 ⁰ C for 8 h. It was discharged to 50 ml of water and precipitated by the addition of sodium perchlorate. After aspirating, 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 ⁰ C in a vacuum. 0.3 g (95% of theory) of a red powder of the formula (IIa)

of mp.> 280 ⁰ C.

X _n13x = 542, 578 nm (dimethylformamide) ε = 105444 1 / mole cm (at 578 nm)

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

Example 6

Analogously to Example 4, using thiophene-2-sulfonic acid chloride (J. Chem. Soc. 1956, 4114) the metal complex of the formula

produced.

M.p.> 280 ⁰ C

λ _m a _x = 555 nm (methylene chloride)

ε = 59084 1 / mole cm

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol)

gives a glassy film

Example 7

12.7 g of the azo dye from Example 5a) were initially charged in 50 ml of acetone tril and mixed with 1.35 g of nickel acetate tetrahydrate. After stirring overnight at room temperature

0.5 ml of dimethyl sulfate and stirred again overnight at room temperature. 0.64 g

Lithium perchlorate was interspersed. After stirring for 30 minutes, it was slowly added to 100 ml Water discharged. After aspirating, washing with 10 ml of water and drying at 50 ⁰ C in vacuo gave 4.8 of a purple powder of mp. 309 ⁰ C (dec.).

It is a mixture of metal complexes of formers

λ _max = 543, 578 nm (dichloromethane)

Solubility:> 2% in TFP (2,2,3,3-tetrafluoropropanol) glassy film.

Example 8

It became at room temperature a solution of the concentration of 20 g / l of a

Dye mixture prepared in 2,2,3,3-tetrafluoropropanol. The dye mixture consisted of three parts by mass of the azo metal complex of the formula (IIIa) of Example 1 and two parts by mass of the azo metal complex of the formula (LIVa) of Example 4. This solution was applied by spin coating on a pregrooved polycarbonate substrate. The pregrooved polycarbonate substrate was made by injection molding as a disk. The

Dimensions of the disk and groove structure were the same as those commonly used for DVD + R. The disk with the dye layer as information carrier was vapor-deposited with 100 nm of silver. Subsequently, a second disk was glued to the silver layer of the first with UV-curable acrylic paint. The thus-finished disc was burned by a commercial burner Plextor PX-708US at 4 times speed. The written data on the disk was analyzed by a reference drive (Datarius CS4). 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 (LHIa) or (LVa). analog

Results were obtained with the mixtures of the azo metal complex of the formula (LIIa) with one of the azo metal complexes of the formula (LITIa), (LTVa) or (LVa). analog

Results were also obtained when the mixing ratios C ₁ Zc ₂ within the

Limits 1 to 5 were varied. The discs can be written with at least 4x (4x) to at least 8x (8x) write speed.

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 T)

^a) isomer mixture

^b) Mixture of the two symmetric and the asymmetric complex Table 2 (azo metal complexes 2)

^b) Mixture of the two symmetric and the asymmetric complex

Claims

claims

1. Mixtures containing at least two different Azometallkomplexe, the ligands of the formula

wherein

Xl is S or NH,

X 1 and X 1 independently of one another are CH or N,

wherein the χl-containing heterocycle may be substituted by nonionic radicals,

R ^{0 is} NR ² R ^{2 '} , R ⁸ or K ⁺ An,

R and R independently of one another represent optionally substituted by hydroxy, cyano or fluorine-substituted Ci-C _δ- alkyl and

R ^{2 can} additionally be hydrogen,

R ³ and R independently of one another are C ₁ -C ₄ -alkyl optionally 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 and R are hydrogen or

R; R and R; R independently of one another are together a - (CH ₂ V ° of the - (CH ₂ ) 3 bridge,

R ^s is optionally substituted by chlorine, C _j-C4-alkoxy, in particular methoxy, cyano, nitro or acetamino 2- or 3- thienyl,

2-, 3- or 4-pyridyl, pyridine-N-oxide-2,

Is 3- or 4-yl, pyrimidin-2 or 4-yl, benzthiazol-2 or -6-yl,

K ^{+ is} an optionally substituted by chlorine, C ^ -C ^ alkoxy, in particular methoxy, cyano, nitro or aceto-amino-substituted radical of the formula

stands,

R 11 is C 1 -C 4 acyl, in particular methyl, ethyl or benzyl and

An ^{¬ stands} for an anion.

A mixture according to claim 1 comprising at least one azo metal complex bearing at least one ligand of formula (I) wherein

χl is NH and at least one different azometallic complex carrying at least one ligand of the formula (I) wherein

χl is S and the other 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 (DDb)

wherein the radicals have the meanings described in claim 1 or 2.

4. Mixture according to at least one of claims 1 to 3, comprising at least one azometallic complex of at least one ligand of the formula (XI) ₅ (XH) and / or (XHI) possesses

has

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

has,

wherein

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 independently of one another represent methyl, ethyl or 2,2,2-trifluoroethyl and

R ^{2 can} additionally be hydrogen,

R ³ and R ^{4 are} independently methyl, ethyl or

R ^s and R ^{6 are} hydrogen or

R ³ , R ⁵ and R ⁴ ; R ⁶ independently of one another are together a - (CR ₂ ) I- or

- (CH ₂ ) ₃ - bridge stand,

R ^{7 is} methyl or ethyl,

R ^{8 is} 2-thienyl, pyridine-N-oxide-3-yl, 2-, 3- or 4-pyridyl,

R ^{9 is} hydrogen, methyl, trifluoromethyl, chlorine or bromine,

R ^{10 is} trifluoromethyl,

R ^{11 is} methyl, ethyl or benzyl,

R ^{12 is} hydrogen, cyano or nitro and

An ^"stands for an anion,

where the radicals in ligands (XI) to (XV) need not have the same meaning.

5. Mixture according to at least one of claims 1 to 4, characterized in that it comprises at least one azometallic complex of the formula (Ia)

(Ia)

in which the two ligands I independently of one another have the meaning given in claims 1 to 4 and

M stands for a metal.

6. Mixture according to at least one of claims 1 to 5, characterized in that a divalent transition metal, in particular Cu, Ni, Co, Zn, Pd, preferably Cu, Ni and Co, particularly preferably Ni is used as the metal of the azo metal complex.

7. Mixture according to at least one of claims to 4, characterized in that they contain ligands of the formulas (XT), (XTV) and (XV),

wherein

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

stands,

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 and R ⁴ , R ^{6 represent} a -CH ₂ -CH ₂ -CH ₂ -bridge,

R ^{8 is} 2-thienyl, 2- or 3-pyridyl,

R ^{9 is} hydrogen, methyl or bromine, R ^{11 is} methyl and

An ^'stands for an anion.

8. 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:

(XIVc),

(XVc)

(XVIc)

wherein

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

where An ^"stands for an anion.

9. Use of mixtures according to at least one of claims 1 to 8 as a light-absorbing compound in the information layer of once beschreib¬ Baren optical data carriers.

10. Use according to claim 9, characterized in that the optical

Data carrier with red laser light, in particular with a wavelength in the range of 600-700 nm can be described and read.

11. A solution of mixtures according to claim 1, characterized in that it contains at least 1 wt .-% of the mixture according to claim 1 and that as a solvent 2,2,3,3-tetrafluoropropanol, propanol, butanol, pentanol, hexanol,

Diacetone alcohol, dibutyl ether, heptanone or mixtures thereof is used.

12. Solution of mixtures of azo metal complexes according to claim 11, characterized in that 2,2,3,3-tetrafluoropropanol is used as the solvent.

13. Optical data carrier containing a preferably transparent, optionally already coated with one or more reflective layers substrate on the surface of which is a light describable information layer, optionally one or more reflective layers and optionally a protective layer or another substrate or Abdeckscbicht are applied, which can be with red light, preferably laser light, described and read, the information layer 5 a light-absorbing compound and optionally one

Containing binder, characterized in that at least a mixture of two Azometallkomplexen according to at least one of claims 1 to 8 is used as the light-absorbing Ver¬ binding.

14. An optical data carrier according to claim 13 containing a preferably -10 transparent substrate, on the surface of which a light writable

Information layer, a reflective layer, an adhesive layer and another substrate are applied, which can be described and read with red light, preferably laser light, wherein the information layer contains a light-absorbing compound, characterized in that the light-absorbing compound according to a mixture of two Azometallkomplexen after at least one of claims 1 to 8 is used.

15. Optical data carrier according to at least one of claims 13 or 14, characterized in that a mixture according to claim 4 is used as the light-absorbing compound.

20 16. A method for producing the optical data carrier according to at least one of

Claims 13 to 15, which is characterized in that a preferably transparent substrate with a mixture according to claim 1, optionally in combination with suitable binders and additives and optionally suitable solvents and optionally coated with a reflective layer, a

25 adhesive layer and another substrate provides.

17 with red light, in particular red laser light, described optical data carrier according to at least one of claims 13 to 15.