EP1599548A1 - Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques - Google Patents

Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques

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Publication number
EP1599548A1
EP1599548A1 EP04707150A EP04707150A EP1599548A1 EP 1599548 A1 EP1599548 A1 EP 1599548A1 EP 04707150 A EP04707150 A EP 04707150A EP 04707150 A EP04707150 A EP 04707150A EP 1599548 A1 EP1599548 A1 EP 1599548A1
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EP
European Patent Office
Prior art keywords
optionally substituted
substituted
independently
methyl
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP04707150A
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German (de)
English (en)
Inventor
Horst Berneth
Friedrich-Karl Bruder
Rainer Hagen
Karin HASSENRÜCK
Serguei Kostromine
Christa-Maria KRÜGER
Timo Meyer-Friedrichsen
Rafael Oser
Josef-Walter Stawitz
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Publication of EP1599548A1 publication Critical patent/EP1599548A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/20—Monoazo compounds containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/18—Monoazo compounds containing copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/22—Monoazo compounds containing other metals

Definitions

  • Metal complexes as light-absorbing compounds in the information layer of optical data carriers are Metal complexes as light-absorbing compounds in the information layer of optical data carriers
  • the invention relates to metal complexes, a process for their preparation, the azo compounds functioning as ligands of the metal complexes and their production, the coupling components on which the azo compounds are based and their production, and optical data memories which contain the metal complexes in their information layer, and the application of the dyes mentioned above a polymer substrate, in particular polycarbonate, by spin coating or vapor deposition.
  • the write-once optical data carriers using special light-absorbing substances or their mixtures are particularly suitable for use in high-density writable optical data memories which work with blue laser diodes, in particular GaN or SHG laser diodes (360 - 460 nm) and / or for the Use with DVD-R (DVD-R, DVD + R) or CD-R discs that work with red (635 - 660 nm) or infrared (780 - 830 nm) laser diodes.
  • the next generation of optical data storage media - the DVD - is currently being launched on the market.
  • the storage density can be increased by using shorter-wave laser radiation (635 to 660 nm) and a higher numerical aperture NA.
  • the recordable format in this case is the DVD-R.
  • 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 sufficient sensitivity when use the fact that the IR wavelength 780 nm of the CD-R lies at the foot of the long-wave flank of the absorption peak of the dye, the red wavelength 635 nm and 650 nm of the DVD-R (DVD-R, DVD + R ) lies at the foot of the short-wave edge of the absorption peak of the dye.
  • This concept is described in JP-A 02 557 335, JP-A 10 058 828, JP-A 06 336086, JP-A 02 865 955, WO-A 09 917284 and US-A 5 266 699 in the 450 nm range
  • the writable information layer made of light-absorbing organic substances must have a morphology which is as amorphous as possible in order to keep the noise signal as small as possible when writing or reading.
  • the substances are applied by spin coating from a solution, by vapor deposition and / or sublimation, subsequent crystallization of the light-absorbing substances with metallic or dielectric layers in vacuum is prevented.
  • the amorphous layer of light-absorbing substances should preferably have a high heat resistance, since otherwise other layers of organic or inorganic material, which are applied to the highly absorbing information layer by sputtering or vapor deposition, form blurred interfaces via diffusion and thus adversely affect the reflectivity.
  • a light-absorbing substance with too low heat resistance at the interface to a polymer carrier can diffuse in it and in turn adversely affect the reflectivity.
  • An excessively high vapor pressure of a light-absorbing substance can sublimate 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.
  • the object of the invention is therefore to provide suitable compounds that are high
  • the invention therefore relates to metal complexes which have at least one ligand of the formula ( ⁇ )
  • X 1 represents O, S, NR 1 or CH,
  • a together with X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,
  • R 1 for hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted
  • R 2 and R 3 are independently hydrogen, optionally substituted C ⁇ -C ⁇ 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 5 -C ⁇ 2 - ⁇ alkenyl, optionally substituted C 2 -C ⁇ 2 alkynyl, optionally substituted C 7 -C 2 aralkyl, optionally substituted C o -Cio aryl or a five- or six-membered heterocyclic ring or
  • Ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • R 4 and R 5 independently of one another represent hydrogen, halogen, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 1 -C 6 alkoxy, optionally substituted CC 6 alkylthio or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SCVY 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 , Y 2 and Y 3 independently of one another for optionally substituted C Ci 2 alkyl, optionally substituted G ⁇ -Cio-Arvl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR 6 , -NH-R 6 or NR 6 R 7 stand or Y 2 and Y 3 stand together for a bridge,
  • R 6 and R 7 independently of one another are optionally substituted -C ⁇ alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ⁇ 2 alkenyl, optionally substituted C 2 -C ⁇ 2 alkynyl, optionally substituted C 7 -C ⁇ 2 aralkyl, optionally substituted C ⁇ -Cio-aryl or a five- or six-membered heterocyclic ring or
  • Ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • X 2 represents N or CH
  • the metal complexes are present as 1: 1 or 1: 2 metalhazo complexes.
  • Preferred metal complexes are those which are characterized in that they have the formula (Ia) [(,)] 2+
  • M stands for a metal
  • M stands for a metal
  • Preferred metals are divalent metals, transition metals or rare earths, in particular Mg, Ca, Sr, Ba, Cu, Ni, Co, Fe, Zn, Pd, Pt, Ru, Th, Os, Sm, Eu.
  • the metals Pd, Fe, Zn, Cu, Ni and Co. are preferred.
  • Ni and Zn are particularly preferred.
  • metals are trivalent metals, transition metals or rare earths.
  • the excess third charge of the metal is compensated for by an anion.
  • B, Al, Ga, In, V, Co, Cr, Fe, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb are particularly suitable.
  • B, Al, Co. are preferred.
  • Co. is particularly preferred.
  • Halogen in particular Cl or F, nitro, cyano, hydroxy, CO-NH 2, CO-O-alkyl or alkoxy, come in as possible substituents of the alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl, aryl or hererocyclic radicals Question.
  • the alkyl radicals can be straight-chain or branched and they can be partially or perhalogenated. Examples of substituted alkyl radicals are trifluoromethyl, chloroethyl, cyanoethyl, methoxyethyl. Examples of branched alkyl radicals are
  • Preferred optionally substituted C 1 -C 4 -alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, octyl, decyl, dodecyl , perfluorinated methyl, perfluorinated ethyl, 3,3,3-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, perfluorobutyl, cyanoethyl, methoxyethyl.
  • Examples of preferred aralkyl include benzyl, phenethyl or phenylpropyl.
  • Preferred heterocyclic radicals are furyl, thienyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl, imidazolyl, benzimidazolyl, pyridyl, pyrimidyl, pyrazinyl, quinolyl, which can be substituted by methyl, methoxy, chlorine, cyano, nitro or methoxycarbonyl.
  • They are preferably colorless anions.
  • Suitable anions are, for example, chloride, bromide, iodide, nitrate, tetrafluoroborate, perchlorate, hexafluorosilicate, hexafluorophosphate, methosulfate, ethosulfate, Q- to Cio-alkanesulfonate, C to Cio-perfluoroalkanesulfonate, optionally by chlorine, hydroxy, - to C 4 - alkoxy substituted Ci to Cio alkanoate, optionally by nitro, cyano, hydroxy, - bis
  • Benzoate the anion of naphthalenedicarboxylic acid, diphenyl ether disulfonate, tetraphenyl borate, cyanotriphenyl borate, tetra-Ci to C 2 o-alkoxyborate, tetraphenoxyborate, 7,8- or 7,9-dicarbanidoundecaborate (l-) or (2-), which may be given to the B and / or C atoms are substituted by one or two C 1 to C 2 alkyl or phenyl groups, dodecahydro dicarbadodecaborate (2-) or BC to C 2 alkyl C-phenyl dodecahydro dicarbadodecaborate ( l)
  • Polystyrene sulfonate poly (meth) acrylate, polyallylsulfonate. Bromide, iodide, tetrafluoroborate, perchlorate, hexafluorophosphate, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, toluenesulfonate, dodecylbenzenesulfonate, tetradecanesulfonate, polystyrene sulfonate are preferred.
  • An "all monovalent anions or one equivalent of a polyvalent anion of a dye can be used.
  • the anionic dye to" an absorption spectrum similar to the cationic azo metal salt. Suitable examples are anionic azo dyes, anthraquinone dyes, porphyrins, phthalocyanines, subphthalocyanines, cyanines, merocyanines, rhodamines, metal complexes and oxonols.
  • Piperazino or Piperidino can be substituted
  • X 1 represents O, S, NR 1 or CH.
  • R 1 represents hydrogen, Q to C 4 alkyl, allyl or C 7 to C 9 aralkyl,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y 2 and Y 3 independently of one another for methyl, ethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
  • 2,2-difluoroethyl, phenyl, tolyl, -OR 6 , -NH-R 6 or NR 6 R 7 or Y 2 and Y 3 together represent a ⁇ (CH 2 ) 4 -, - (CH 2 ) 5 - or -CH 2 -CH CH-CH 2 bridge,
  • R 6 and R 7 independently of one another, optionally by fluorine, chlorine, hydroxy, methoxy,
  • NR 6 R 7 represents pyrrolidino, piperidino or morpholino
  • benzthiazol-2-yl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro
  • benzimidazol-2-yl which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted
  • thiazol-2-yl which is replaced by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl
  • Methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH 2 ) 4 - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different chlorine radicals , Fluorine, methoxy, methylthio, phenyl or cyano can be substituted, imidazol-2-yl, which can be substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl,
  • Cyanethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-ph ⁇ nylamino, anilino, pyrrolidino, piperidino or morpholino can be substituted, l, 2,4-thiadiazole -5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, l, 2,4-thiadiazol-3-yl, which can be substituted by methyl or phenyl, 1 , 3,4-triazole
  • 2-yl which can be substituted by methyl or phenyl
  • 2-pyridyl which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro
  • 2-quinolyl which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or Nitro can be substituted
  • 2-pyrimidyl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-
  • X 1 represents O, S, NR 1 or CH,
  • R 1 represents hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or phenylpropyl,
  • R 2 and R 3 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chlorophenyl or anisyl or NR 2 R 3 represents pyrrolidino, piperidino or morpholino,
  • R 4 represents hydrogen, chlorine, methyl, methoxy or methylthio
  • R 5 represents hydrogen or methyl
  • R 2 ; R 4 and R 3 ; R 5 independently of one another are - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (CH 3 ) 2-CH 2 -CH (CH 3 ) - or -0 (CH 2 ) 2 -,
  • Y stands for SO 2 -Y 1 or POY 2 Y 3 ,
  • Y 1 represents -NH-R 6 or -NR 6 R 7 ,
  • Y 2 and Y 3 are the same and represent methyl, ethyl, -OR 6 , -NH-R 6 or -NR 6 R 7 or Y 2 and
  • Y 3 together represent a - (CH 2 ) bridge, or
  • Y 2 represents phenyl
  • Y 3 represents -OR 6 , -NH-R 6 or -N ⁇ 7 ,
  • R 6 and R 7 independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-
  • E TR. 7 represents pyrrolidino, piperidino or morpholino
  • M stands for nickel, zinc, copper, cobalt, iron or palladium.
  • Metal complexes of ligands of the formula (I), in particular (Ib), are also very particularly preferred.
  • M represents boron, aluminum or cobalt
  • Suitable rhodamine dyes are those of the formula (C)
  • R 101 and R 103 independently of one another represent hydrogen, methyl or ethyl
  • R and R independently of one another represent a phenyl, naphthyl, benzthiazolyl or benzoxazolyl radical which is substituted by sulfo or carboxy and 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 ⁇ o? independently of one another are - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (CH 3 ) 2 -CH 2 -CH (CH 3 ) - or -0 (CH 2 ) 2 - and
  • R ] 107 represents hydrogen or sulfo.
  • Suitable oxonol dyes are those of the formula (C ⁇ )
  • the rings B and C represent a five- or six-membered, carbocyclic or heterocyclic ring.
  • R 1 * 1 and R 112 independently of one another represent hydrogen or methyl
  • R 1 113 represents methyl or trifluoromethyl
  • R 114 represents cyano, methoxycarbonyl or ethoxycarbonyl
  • R 115 represents phenyl, chlorophenyl or tolyl.
  • Suitable azo metal complex dyes are those of the formula (CH)
  • Y and Y independently of one another represent -O- or -COO-
  • M-101 stands for a divalent or trivalent metal
  • the benzene rings can be benzanellated and / or substituted by nonionic radicals.
  • Nonionic residues are defined above.
  • M preferably represents Ni, Co, Cr, Fe, Cu.
  • Such metal complexes of ligands of the formula ( ⁇ ) are particularly preferred, in particular
  • R 1 represents hydrogen, methyl, ethyl or benzyl
  • R 2 and R 3 independently of one another represent methyl, ethyl, cyanoethyl, cyclohexyl, benzyl or phenyl or
  • NR 2 R 3 represents pyrrolidino, piperidino or morpholino
  • R 4 represents hydrogen, methyl or methoxy
  • R 5 represents hydrogen or
  • R 2 ; R 4 represents - (CH 2 ) 2 - or - (CH 2 ) 3 -,
  • Y stands for SO 2 -Y 1 or POY 2 Y 3 ,
  • Y 1 represents -NH-R 6 or -NRV
  • Y 2 and Y 3 are the same and stand for -OR 6 ,
  • R 6 and R 7 independently of one another are methyl, ethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl,
  • NR 6 R 7 represents pyrrolidino, piperidino or morpholino
  • M stands for nickel, zinc, copper or cobalt.
  • metal complexes of ligands of the formula (I), in particular (Ib), are also extremely preferred.
  • 1,3,4-thiadiazole 5-phenyl-l, 3,4-thiadiazol-2-yl, 5-methyl-l, 3,4-thiadiazole, 2-pyridyl, 2-pyrimidyl, 4-cyano2-pyrimidyl.
  • the metal complexes according to the invention come in particular as powder or granules or as
  • the granulate form is preferred, in particular granules with an average particle size of 50 ⁇ m to 10 mm, in particular especially 100 to 800 ⁇ m.
  • Such granules can be produced, for example, by spray drying.
  • the granules are particularly characterized by their low dust level.
  • the metal complexes according to the invention are notable for good solubility. They are readily soluble in non-fluorinated alcohols. Such alcohols are, for example, those with 3 to 6 carbon atoms, preferably propanol, butanol, pentanol, hexanol, diacetone alcohol or else
  • Mixtures of these alcohols such as. B. propanol / diacetone alcohol, butanol / diacetone alcohol, butanol hexanol.
  • Preferred mixing ratios for the listed mixtures are, for example, 80:20 to 99: 1, preferably 90:10 to 98: 2.
  • the concentrated solutions are also preferred. They are at least 1% by weight, preferably at least 2% by weight, particularly preferably at least 5% by weight, of the metal complexes according to the invention, in particular those of the formulas (Ia), (Ib) or (H).
  • 2,2,3,3-tetafluoropropanol, propanol, butanol, pentanol, hexanol, diacetone alcohol, dibutyl ether, heptanone or mixtures thereof are preferably used as solvents.
  • 2,2,3,3-Tetrafluoropropanol is particularly preferred.
  • Butanol is also particularly preferred.
  • Butanol / diacetone alcohol in a mixing ratio of 90:10 to 98: 2 is also particularly preferred.
  • the invention further relates to a process for the preparation of the metal complexes of the formulas (Ia) and (Ib) according to the invention, which is characterized in that a metal salt with an azo compound of the formula (Ic)
  • X 1 represents O, S, NR 1 or CH,
  • X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals, R 1 for hydrogen, optionally substituted -C ⁇ -alkyl, optionally substituted
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted -C ⁇ -alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ⁇ 2 -
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 are independently hydrogen, halogen, optionally substituted C ⁇ -C 6 - alkyl, optionally substituted C ⁇ -C6 alkoxy optionally substituted C ⁇ -C, 6 - alkylthio or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y 2 and Y 3 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted C 6 -C 10 aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR 6 , -NH-R 6 or NR 6 R 7 stand or Y 2 and Y 3 together stand for a bridge,
  • R 6 and R 7 independently of one another are optionally substituted -C ⁇ alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ⁇ 2 alkenyl, optionally substituted C 2 -C ⁇ 2 alkynyl, optionally substituted C 7 -C 2 aralkyl, optionally substituted C 6 -C 0 aryl or a five- or six-membered heterocyclic ring or
  • NR ⁇ 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals, implements.
  • Two or more different azo compounds of the formula (Ic) can also be used in this process according to the invention.
  • a statistical mixture of metal complexes is then obtained, consisting of those complexes which contain two identical ligands of the formula ( ⁇ ) and those complexes which contain two different ligands of the formula (I).
  • metal complexes and the metal complexes themselves are also meant quite analogously if a mixture of azo compounds of the formulas Ic is used in their production.
  • the reaction according to the invention is generally carried out in a solvent or solvent mixture, if appropriate in the presence of basic substances, at room temperature to the boiling point of the solvent, for example at 20-100 ° C., preferably at 20-50 ° C.
  • the metal complexes either precipitate directly and can be isolated by filtration or they are precipitated, for example, by adding water, possibly with partial or complete removal of the solvent beforehand, and isolated by filtration. It is also possible to carry out the reaction directly in the solvent to give the concentrated solutions mentioned above.
  • Metal salts include, for example, the chlorides, bromides, sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, hydroxides, oxides, carbonates, hydrogen carbonates, salts of carboxylic acids such as formates, acetates, propionates, benzoates, salts of
  • Metal salts are also to be understood as meaning complexes with ligands other than those of the formulas (T), in particular complexes of acetylacetone and acetoacetic acid esters.
  • Possible metal salts are, for example: nickel acetate, cobalt acetate, copper acetate, nickel chloride, nickel sulfate, cobalt chloride, copper chloride, copper sulfate,
  • alkali acetates such as. B. sodium acetate, potassium acetate, alkali hydrogen carbonates, carbonates or hydroxides such as sodium hydrogen carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, or amines such as ammonia, dimethylamine, triethylamine, diethanolamine.
  • alkali acetates such as. B. sodium acetate, potassium acetate, alkali hydrogen carbonates, carbonates or hydroxides such as sodium hydrogen carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, or amines such as ammonia, dimethylamine, triethylamine, diethanolamine.
  • metal salts of strong acids such as metal chlorides or sulfates are used.
  • Suitable solvents are water, alcohols such as methanol, ethanol, propanol, butanol, 2,2,3,3-tetrafluoropanol, ethers such as dibutyl ether, dioxane or tetrahydrofuran, aprotic solvents such as dimethylformamide, N-methylpyrrolidone, acetonitrile, nitromethane, dimethyl sulfoxide , Methanol, ethanol and 2,2,3,3-tetrafluoropropanol are preferred.
  • the salt-like metal complexes of the formula (Ib) can also be prepared by
  • Oxidation of metal complexes of the formula (Ia) can also be carried out by reacting azo dyes of the formula (Ic) with salts of divalent metals in the presence of an oxidizing agent.
  • Suitable oxidizing agents are, for example, nitric acid, nitrous acid, hydrogen peroxide, Caro's acid, alkali peroxodisulfates, alkali perborates, air, oxygen. Are preferred
  • azo compounds of the formula (Ic) required for the preparation of the metal complexes according to the invention are also the subject of this invention. Some of them are known from EP-A 0 040 171.
  • the invention therefore also relates to azo compounds of the formula (Ic)
  • X 1 represents O, S, NR 1 or CH,
  • a together with X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,
  • R 1 represents hydrogen, optionally substituted -C ⁇ -alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ⁇ 2 alkenyl or optionally substituted C 7 -C ⁇ 2 aralkyl, R 2 and R 3 independently of one another for hydrogen, optionally substituted CC 12 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ] 2 -
  • Alkenyl optionally substituted C 2 -C 12 alkynyl, optionally substituted C 7 -
  • Ci 2 aralkyl optionally substituted C 6 -C 10 aryl or a five- or six-membered heterocyclic ring or
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 are independently hydrogen, halogen, optionally substituted C ⁇ -C 6 - alkyl, optionally substituted C ⁇ -C 6 -alkoxy, unsubstituted or substituted C ⁇ -C 6 -
  • Alkylthio stand or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR'TR 7 ,
  • Y 2 and Y 3 independently represent optionally substituted C ⁇ -C12 alkyl, optionally substituted C 6 -C ⁇ 0 aryl, an optionally substituted five- or six-membered aromatic or quasi-aromatic heterocyclic group, -OR 6, -NH-R 6 or NR 6 R 7 or Y 2 and Y 3 together represent a bridge,
  • R 6 and R 7 independently of one another, for optionally substituted CC J2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 - C] 2 aralkyl, optionally substituted C 6 -C ⁇ 0 aryl or a five- or six-membered hetero- cyclic ring stand or
  • NR 6 R 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals.
  • benzthiazol-2-yl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro
  • benzimidazol-2-yl which can be substituted by up to three identical or different radicals of the series chlorine, methyl
  • Methoxy, ethoxy, cyano or nitro can be substituted, thiazol-2-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH 2 ) - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methoxy,
  • Methylthio, methanesulfonyl, phenyl, dimethylamino or anilino may be substituted, l, 2,4-thiadiazol-3-yl, which may be substituted by methyl or phenyl, 1,3,4-triazol-2-yl, which may be substituted by methyl or Phenyl may be substituted, 2-pyridyl which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-quinolyl which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-pyrimidyl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-triazin-2-yl or 2-pyrazinyl,
  • X 1 represents O, S, NR 1 or CH.
  • R 1 represents hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or
  • R 2 and R 3 independently of one another are hydrogen, methyl, ethyl, propyl, butyl,
  • NR 2 R 3 represents pyrrolidino, piperidino or morpholino
  • R 4 represents hydrogen, chlorine, methyl, methoxy or methylthio
  • R 5 is hydrogen or methyl
  • R 2 ; R 4 and R 3 ; R 5 independently of one another are - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (CH 3 ) 2 -CH 2 -CH (CH 3 ) - or -0 (CH 2 ) 2 -,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -NH-R 6 or -NR 6 R 7 ,
  • Y 2 and Y 3 are the same and represent methyl, ethyl, -OR 6 , -NH-R 6 or -NV or Y 2 and
  • Y 3 together represent a - (CH 2 ) 4 bridge, or
  • Y 3 represents -OR 6 , -NH-R 6 or -M * R 7 ,
  • R 6 and R 7 independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-
  • NR 6 R 7 represents pyrrolidino, piperidino or morpholino.
  • the invention also relates to a process for the preparation of the azo compounds of the formula (Ic) according to the invention, which is characterized in that an amino heterocycle of the formula (IV)
  • X 1 represents O, S, NR 1 or CH
  • a together with X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,
  • R 1 represents hydrogen, optionally substituted CC 12 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl or optionally substituted C 7 -C 2 aralkyl,
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C ] 2 -
  • Alkenyl optionally substituted C 2 -C 2 alkyl, optionally substituted C -
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 independently of one another for hydrogen, halogen, optionally substituted Q-C ⁇ -alkyl, optionally substituted C ⁇ -C 6 alkoxy, optionally substituted Ci-Ce-
  • Alkylthio stand or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for S0 2 -Y 'or POY 2 Y 3
  • Y 1 represents -OR 6 , -NH-R 6 or NR'TR 7 ,
  • Y 2 and Y 3 independently of one another for optionally substituted C 1 -C 2 -alkyl, optionally substituted C 6 -C 10 -aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR 6 , -NH-R 6 or NR ⁇ 7 stand or Y 2 and Y 3 stand together for a bridge,
  • R 6 and R 7 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7-Ci2 aralkyl, optionally substituted C 6 -C ⁇ 0 aryl or a five- or six-membered hetero- cyclic ring stand or
  • NR ⁇ 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Another object of the invention is a method for producing the invention
  • X 1 represents NH
  • a together with X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted C 7 -
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 are independently hydrogen, halogen, optionally substituted Cj-C 6 - alkyl, optionally substituted C ⁇ -C 6 -alkoxy, optionally substituted C] -C 6 - alkylthio or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y 2 and Y 3 independently of one another for optionally substituted -Ciz-alkyl, optionally substituted C 6 -C ⁇ o-aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR 6 , -NH-R 6 or NR '' TR 7 stand or Y 2 and Y 3 stand together for a bridge,
  • R 6 and R 7 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -Ci 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 -C 2 aralkyl, given appropriate, substituted C 6 -C ⁇ 0 aryl or a five- or six-membered heterocyclic ring or
  • NR ⁇ R. 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and or which may be substituted by nonionic radicals,
  • R represents optionally substituted C 1 -C 2 -alkyl, optionally substituted C 3 -C 8 cycloalyl, optionally substituted C 2 -C 2 alkenyl or optionally substituted C -C 2 aralkyl,
  • Z represents a leaving group
  • R * -Z stands for example for an alkyl or aralkyl chloride, bromide, iodide, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate, tolulsulfonate or a sulfuric acid alkyl or aralkyl ester. Examples are methyl iodide, benzyl bromide, dimethyl sulfate, toluenesulfonic acid ethyl ester.
  • the basic substances listed above are suitable as basic substances.
  • the invention further relates to the coupling component of the formula (V)
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C] -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 independently of one another represent hydrogen, halogen, optionally substituted C 1 -C 6 -alkyl, optionally substituted C 1 -C 6 -alkoxy, optionally substituted C 1 -C 6 -alkylthio or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y 2 and Y 3 independently represent optionally substituted C ⁇ -C12 alkyl, optionally substituted C 6 -C ⁇ 0 aryl, an optionally substituted five- or six-membered aromatic or quasi-aromatic heterocyclic group, -OR 6, -NH-R 6 or NR 6 R 7 or Y 2 and Y 3 together represent a bridge,
  • R 6 and R 7 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 -C 2 aralkyl, given optionally substituted C ⁇ -Cio-aryl or a five- or six-membered heterocyclic ring or
  • NR'T 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals.
  • R 6 represents a fluorine-substituted ethyl, propyl or butyl radical, in particular 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl and
  • R 7 is methyl, ethyl or a fluorine-substituted ethyl, propyl or
  • Butyl radical stands in particular for 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2,2,3,3-tetrafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 4H-hexafluorobutyl.
  • the invention also relates to a process for the preparation of coupling components of the formula V, which is characterized in that
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 -
  • R 4 and R 5 independently of one another for hydrogen, halogen, optionally substituted Q- - alkyl, optionally substituted -C ⁇ -alkoxy, optionally substituted - -
  • Alkylthio stand or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Z 1 represents chlorine or bromine
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y and Y 3 independently represent optionally substituted C ⁇ -C ⁇ 2 alkyl, optionally substituted C 6 -C ⁇ 0 aryl, an optionally substituted five- or six-membered quasi-aromatic, or aromatic heterocyclic group, -OR 6, -NH-R 6 or NR ⁇ 7 stand or Y 2 and Y 3 stand together for a bridge,
  • R 6 and R 7 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted -Cs cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 -C 4 2- aralkyl, optionally substituted C ⁇ -cio-aryl or a five- or six-membered heterocyclic ring or
  • R ⁇ 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • the invention also relates to a process for the preparation of coupling components of the formula V, in which Y represents POY 2 Y 3 , which is characterized in that
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted Ci-C ⁇ -alkyl, optionally substituted C 3 -C 3 cycloalkyl, optionally substituted C 2 -C ⁇ 2 -
  • Alkenyl optionally substituted C 2 -C 2 alkynyl, optionally substituted
  • NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 independently of one another for hydrogen, halogen, optionally substituted Ci-Cg-alkyl, optionally substituted C ⁇ -C 6 alkoxy, optionally substituted Ci-Cg-
  • Alkylthio stand or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y 2 and Y 3 independently of one another represent -OR 6 , -NH-R 6 or NR, R 6 and R 7 independently of one another for optionally substituted C] -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 -C 12 aralkyl, optionally substituted C 6 -C aro or a five- or six-membered heterocyclic ring or
  • NR 6 R 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • the invention also relates to a process for the preparation of coupling components of the formula V, in which Y represents SOzY 1 , which is characterized in that
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkyl, optionally substituted C 7 -C 2 aralkyl, optionally substituted C 6 -C 10 aryl or a five- or six-membered heterocyclic ring or
  • Ring which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • R 4 and R 5 independently of one another represent hydrogen, halogen, optionally substituted C 1 -C 6 -alkyl, optionally substituted CC 6 alkoxy, optionally substituted CC 6 alkylthio or R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • R 6 and R 7 independently of one another for optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 -C ⁇ 2 -aralkyl, where appropriate substituted C 6 -C ⁇ 0 aryl or a five- or six-membered heterocyclic ring or
  • NR 6 R 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 3 and R 4 ⁇ H are preferred for reaction. These reactions can be carried out in the presence of a base, for example a tertiary amine or a sodium or potassium hydroxide, hydrogen carbonate or carbonate.
  • a base for example a tertiary amine or a sodium or potassium hydroxide, hydrogen carbonate or carbonate.
  • the coupling component of the formula (V) is thus obtained in free form, as an HC1 or HBr salt.
  • Suitable solvents are 1,2-dichloroethane, carbon tetrachloride, toluene, but also alcohols such as methanol or ethanol and water.
  • the invention further relates to the use of the metal complexes according to the invention as highly absorbent compounds in the hiformation layer of once writable optical
  • the optical data carrier is preferably written and read with blue laser light, in particular with a wavelength in the range of 360-460 nm.
  • the optical data carrier is also preferably written to and read with red laser light, in particular with a wavelength in the range from 600-700 nm.
  • the invention further relates to the use of metal complexes with azo ligands as a highly absorbent compound in the formation layer of write-once optical data carriers, the optical data carrier being able to be written and read with blue laser light, in particular with a wavelength in the range of 360-460 nm.
  • the invention further relates to an optical data carrier containing a preferably transparent substrate, optionally already coated with one or more reflective layers, on the surface of which an information layer which can be written on with light, optionally one or more reflective layers and optionally a protective layer or a further substrate or a covering layer are applied which is particularly preferred with a blue, preferably with a wavelength in the range of 360-460 nm, in particular 390 to 420 nm added from 400 to 410 nm, or red light, preferably with a wavelength in the range of 600-700 nm, preferably from 620 to 680 nm, very particularly preferably from 630 to 660 nm, preferably laser light, can be written and read,
  • the Information layer contains a high-absorption compound and optionally a binder, characterized in that at least one according to the invention as the high-absorption compound
  • the highly absorbent compound should preferably be thermally changeable.
  • the thermal change preferably takes place at a temperature ⁇ 600 ° C., particularly preferably at a temperature ⁇ 400 ° C., very particularly preferably at a temperature ⁇ 300 ° C., in particular ⁇ 200 ° C.
  • Such a change can be, for example, a decomposition or chemical change in the chromophoric 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 embodiment of the metal complex according to the invention.
  • the light-absorbing compounds used are those of the formulas (Ia) or (Ib),
  • X 1 represents O, S, NR 1 or CH,
  • a together with X 1 and N represents a five- or six-membered aromatic or quasi-aromatic heterocyclic ring which contains 1 to 4 heteroatoms and / or benzylated or naphthanellated and / or can be substituted by nonionic radicals,
  • R 1 represents hydrogen, optionally substituted C 1 -C 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl or optionally substituted C 7 -C 2 aralkyl,
  • R 2 and R 3 independently of one another for hydrogen, optionally substituted C 1 -C 12 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 - Ciz-aralkyl, optionally substituted C 6 -C ⁇ o-aryl or a five- or six-membered heterocyclic ring or NR 2 R 3 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • R 4 and R 5 are independently hydrogen, halogen, optionally substituted C ⁇ -C 6 - alkyl, optionally substituted C ⁇ -C 6 -alkoxy, unsubstituted or substituted C ⁇ -C 6 -
  • Alkylthio stand or
  • R 2 ; R 4 and R 3 ; R 5 independently of one another represent a two- to four-membered bridge which may contain further heteroatoms and / or which may be substituted by nonionic radicals,
  • Y stands for SO 2 -Y 1 or POY 2 Y 3 ,
  • Y 1 represents -OR 6 , -NH-R 6 or NR 6 R 7 ,
  • Y 2 and Y 3 independently of one another for optionally substituted C 1 -C 2 -alkyl, optionally substituted C 6 -C 10 aryl, an optionally substituted five- or six-membered quasi-aromatic or aromatic heterocyclic radical, -OR 6 , -NH-R 6 or NR ⁇ 7 stand or Y 2 and Y 3 stand together for a bridge,
  • R 6 and R 7 independently of one another, for optionally substituted CrC 2 alkyl, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 2 -C 2 alkenyl, optionally substituted C 2 -C 2 alkynyl, optionally substituted C 7 - C 2 aralkyl, optionally substituted C 6 -C 0 aryl or a five- or six-membered heterocyclic ring or
  • NR 6 R 7 together with the nitrogen atom represents a five- to seven-membered heterocyclic ring which may contain further heteroatoms and / or may be substituted by nonionic radicals,
  • M stands for a metal
  • the light-absorbing compounds used are those of the formula (Ia)
  • benzthiazol-2-yl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro
  • benzimidazol-2-yl which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted
  • thiazol-2-yl which can be substituted by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl, methoxy, phenyl, cyano, nitro , Methoxycarbonyl, methanesulfonyl, formyl or a divalent radical of the formula - (CH) 4 - can be substituted
  • thiazol-4-yl which is replaced by up to two identical or different radicals from the series chlorine, fluorine, methoxy, methylthio, phenyl or cyano can be substituted
  • Methanesulfonyl, phenyl, dimethylamino or anilino may be substituted, 1,3,4-triazol-2-yl, which may be substituted by methyl or phenyl, 2-pyridyl, which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro may be 2-quinolyl, which may be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 2-pyrimidyl, by up to three identical or different radicals from the series
  • Chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro can be substituted, 1,3,5-triazin-2-yl or 2-pyrazinyl is present,
  • X 1 represents O, S, NR 1 or CH.
  • Phenylpropyl stands, R 2 and R 3 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chloropehnyl or anisyl or
  • NR 2 R 3 represents pyrrolidino, piperidino or morpholino
  • R 4 represents hydrogen, chlorine, methyl, methoxy or methylthio
  • R 5 represents hydrogen or methyl
  • R 2 ; R 4 and R 3 ; R 5 independently of one another are - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (CH 3 ) 2 -CHz-CH (CH 3 ) - or -0 (CH 2 ) z-,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -NH-R 6 or -NR 6 R 7 ,
  • Y 2 and Y 3 are the same and represent methyl, ethyl, -OR 6 , -NH-R 6 or -NR 6 R 7 or Y 2 and Y 3 together represent a - (CH 2 ) 4 bridge or
  • Y 2 represents phenyl
  • Y 3 represents -OR 6 , -NH-R 6 or -NR'Tt 7 ,
  • R 6 and R 7 independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-
  • NR ⁇ 7 represents pyrrolidino, piperidino or morpholino
  • M stands for nickel, zinc, copper, cobalt, iron or palladium.
  • the light-absorbing compounds used are those of the formula (Ib)
  • benzthiazol-2-yl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, ethoxy, cyano or nitro
  • benzimidazol-2-yl which can be substituted by up to three identical or different radicals the series chlorine, methyl, methoxy, ethoxy, cyano or nitro can be substituted
  • thiazol-2-yl which is replaced by up to two identical or different radicals from the series chlorine, fluorine, methyl, trifluoromethyl
  • Methoxy, phenyl, cyano, nitro, methoxycarbonyl, methanesulfonyl, formyl or a bivalent radical of the formula - (CH 2 ) 4 - can be substituted, thiazol-4-yl, which can be substituted by up to two identical or different chlorine radicals , Fluorine, methoxy, methylthio, phenyl or cyano can be substituted, jmidazol-2-yl, which can be substituted by up to two identical or different radicals from the series fluorine, chlorine, methyl, trifluoromethyl,
  • Cyanethylamino, N, N-biscyanethylamino, N-methyl-N-hydroxyethylamino, N-methyl-N-benzylamino, N-methyl-N-phenylamino, anilino, pyrrolidino, piperidino or Mo ⁇ holino can be substituted, l, 2,4-thiadiazole -3-yl, which can be substituted by methyl or phenyl, l, 2,4-thiadiazol-5-yl, which can be substituted by chlorine, methyl, methoxy, phenoxy, methylthio, methanesulfonyl, phenyl, dimethylamino or anilino, 1 , 3,4-triazole
  • 2-yl which can be substituted by methyl or phenyl
  • 2-pyridyl which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro
  • 2-quinolyl which can be substituted by chlorine, methyl, methoxy, cyano, methoxycarbonyl or Nitro
  • 2-pyrimidyl which can be substituted by up to three identical or different radicals from the series chlorine, methyl, methoxy, cyano, methoxycarbonyl or nitro, 1,3,5-
  • X 1 represents O, S, NR 1 or CH.
  • R 1 represents hydrogen, methyl, ethyl, propyl, butyl, allyl, benzyl, phenethyl or phenylpropyl,
  • R 2 and R 3 independently of one another represent hydrogen, methyl, ethyl, propyl, butyl, hydroxyethyl, cyanoethyl, cyclopentyl, cyclohexyl, allyl, benzyl, phenethyl, phenylpropyl, phenyl, tolyl, chlorophenyl or anisyl or NR 2 R 3 represents pyrrolidino, piperidino or Mo ⁇ holino,
  • R 4 represents hydrogen, chlorine, methyl, methoxy or methylthio
  • R 5 represents hydrogen or methyl
  • R 2 ; R 4 and R 3 ; R 5 independently of one another are - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (CH 3 ) 2 -CH 2 -CH (CH 3 ) - or -0 (CH 2 ) 2 -,
  • Y stands for SOz-Y 1 or POY 2 Y 3 ,
  • Y 1 represents -NH-R 6 or -NR 6 R 7 ,
  • Y 2 and Y 3 are the same and represent methyl, ethyl, -OR 6 , -NH-R 6 or -NR 6 R 7 or Y 2 and
  • Y 3 together represent a - (CH 2 ) 4 bridge or
  • ⁇ 2 represents phenyl
  • Y 3 represents -OR 6 , -NH-R 6 or -NR 6 R 7 ,
  • R 6 and R 7 independently of one another for methyl, ethyl, propyl, butyl, 2,2,2-trifluoroethyl, 2,2-
  • NR ⁇ R 7 represents pyrrolidino, piperidino or Mo ⁇ holino
  • M represents boron, aluminum or cobalt
  • such high-absorbing compounds are preferred whose absorption maximum A- ⁇ x z is in the range 420 to 550 nm, the wavelength ⁇ 1/2 , at which is the extinction in the short-wave flank of the absorption maximum of the wavelength ⁇ m ⁇ half the extinction value at A - ⁇ , and the wavelength ⁇ / ⁇ 0 , at which the extinction in the short-wave flank of the absorption maximum of the wavelength ⁇ ⁇ ⁇
  • Such a high-absorbency compound preferably has up to one Wavelength of 350 nm, particularly preferably up to 320 nm, very particularly preferably up to 290 nm, no shorter-wave maximum ⁇ ⁇ .
  • Highly absorbent compounds with an absorption maximum ⁇ ⁇ a a of 430 to 550 nm, in particular 440 to 530 nm, very particularly preferably 450 to 520 nm are preferred.
  • the distances are preferably not more than 70 nm, particularly preferably not more than 50 nm, very particularly preferably not more than 40 nm.
  • Wavelength ⁇ ) / 2 at which the absorbance in the long-wave flank of the absorption maximum of the wavelength is, and the wavelength ⁇ ⁇ 0 , at which the extinction in the long-wave flank of the absorption maximum of the wavelength 7 ⁇ . is a tenth of the absorbance value at A ⁇ , preferably not more than 60 nm apart.
  • Such a high-absorbency compound preferably has up to one
  • These high-absorption compounds ⁇ / 2 and ⁇ / ⁇ 0 are preferably not more than 50 nm apart, particularly preferably not more than 40 nm apart, very particularly preferably not more than 30 nm apart.
  • the highly absorbent compounds preferably have a molar extinction coefficient ⁇ > 30,000 l / mol cm, preferably> 50,000 l / mol cm, particularly preferably> 70,000 l / mol cm, very particularly preferably> 100,000 l / mol cm.
  • Suitable highly absorbent compounds with the required spectral properties are, in particular, those which have a low solvatochromism (dioxane DMF or methylene chloride / methanol).
  • Preferred are metal complexes whose solvatochromism ⁇ DD
  • , ie the positive difference of the absorption wavelengths in the solvents dimethylformamide and dioxane, or whose solvatochromism ⁇ A MM I ⁇ Methanoi - ⁇ M ethyie n c h iorid
  • azo metal complexes according to the invention can also be used with other light-absorbing materials.
  • Compounds are mixed. Highly absorbing compounds with similar spectral properties are preferably selected for this purpose.
  • Such light-absorbing compounds can originate, for example, from the following classes of dyes: cyanines, (diaza) hemicyanines, merocyanines, rhodamines, azo dyes, polyphyrins, phthalocyanines, subphthalocyanines, azo metal complexes. Other azo metal complexes are preferred.
  • the light-absorbing compounds used according to the invention guarantee a sufficiently high reflectivity (> 10%, in particular> 20%) of the optical data carrier in the blank state and a sufficiently high absorption for the thermal degradation of the information layer in the case of selective illumination with focused light if the light wavelength is in the
  • Range is from 360 to 460 nm and 600 to 680 nm.
  • the contrast between written and unwritten points 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 thermal degradation.
  • the light-absorbing compounds used according to the invention have a high light resistance of the unwritten optical data carrier and of the information written on the data carrier against daylight, sunlight or under increased artificial radiation to imitate daylight.
  • the light-absorbing compounds used according to the invention also have a high sensitivity of the optical data carrier to blue and red laser light
  • the light-absorbing compounds used according to the invention are stable enough so that the disk produced with them generally fulfills the required climatic tests.
  • the metal complexes according to the invention are preferably applied to the optical data carrier by spin coating or vacuum evaporation, in particular spin coating. They can be mixed with one another or with other dyes with similar spectral properties.
  • the information layer can contain additives such as binders, wetting agents, stabilizers, thinners and sensitizers and further constituents.
  • the optical data storage device can carry further layers such as metal layers, dielectric layers and protective layers.
  • Metals and dielectric layers serve u. a. to adjust the reflectivity and the heat balance. Depending on the laser wavelength, metals can be gold, silver, aluminum and the like. a. his.
  • 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 consist of acrylic adhesives.
  • the optical data carrier according to the invention has, for example, the following layer structure (cf. FIG. 1): a transparent substrate (1), optionally a protective layer (2), an information layer (3), optionally a protective layer (4), optionally an adhesive layer ( 5), one
  • the structure of the optical data carrier can preferably:
  • a transparent substrate (1) on the surface of which at least one information layer (3) which can be written on with light and which can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.
  • a preferably transparent substrate (1) on the surface of which a protective layer (2), at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied
  • a preferably transparent substrate (1) on the surface of which there is optionally a protective layer (2), at least one information layer (3) that can be written on with light, preferably laser light, optionally a protective layer (4), optionally an adhesive layer (5), and a transparent cover layer (6) are applied.
  • a preferably transparent substrate (1) on the surface of which at least one information layer (3) which can be written on with light, preferably laser light, optionally an adhesive layer (5), and a transparent cover layer (6) are applied.
  • the optical data carrier has, for example, the following layer structure (cf. FIG. 2): 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 invention further relates to optical data carriers according to the invention described with blue or red light, in particular laser light, in particular red laser light.
  • a further 0.1 g of metal complex of the above formula could be isolated by adding 2 ml of water to the mother liquor.
  • Suitable azometal dyes are listed in the following table:
  • the precipitated dye was filtered off with suction: 0.44 g (82% of theory). It has the formula
  • Suitable azometal dyes are listed in the following table:
  • a solution of 2.2 g of dye 1 in 100 ml of 2,2,3,3-tetrafluoropropanol was prepared at room temperature. This solution was applied to a pregrooved polycarbonate substrate using spin coating.
  • the pregrooved polycarbonate substrate was produced as a disk using injection molding. The dimensions of the disc and the groove structure corresponded to those which are usually used for DVD-R.
  • the disk with the dye layer as the information carrier was sputtered with 100 nm silver.
  • a UV-curable acrylic lacquer was then applied by spin coating and cured using a UV lamp.
  • the light reflected by the reflection layer of the disk was coupled out of the beam path with the aid of the polarization-sensitive beam splitter mentioned above and focused on a four-quadrant detector by an astigmatic lens.
  • a linear speed a polarization-sensitive beam splitter
  • the write power was applied here as an oscillating pulse sequence (cf. FIG. 3), the disk being alternately irradiated with the above-mentioned write power P- mU e and the read power P read * 0.5 mW.
  • Example 73

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

L'invention concerne des complexes métalliques destinés à des supports de données optiques, lesdits supports étant pourvus d'un substrat de préférence transparent, préalablement revêtu d'une ou plusieurs couches de réflexion, dont la surface reçoit une couche d'information accessible en écriture au moyen de lumière, éventuellement une ou plusieurs couches de réflexion et éventuellement une couche de protection ou un autre substrat ou une couche de couverture. Ledit support optique est accessible en écriture et lisible au moyen de lumière bleue, rouge ou infrarouge, de préférence au moyen de lumière laser, ladite couche d'information contenant un composé photoabsorbant et éventuellement un liant. Le support optique selon l'invention est caractérisé en ce qu'au moins un desdits complexes métalliques sert de composé photoabsorbant.
EP04707150A 2003-02-13 2004-01-31 Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques Withdrawn EP1599548A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10305924A DE10305924A1 (de) 2003-02-13 2003-02-13 Metallkomplexe als lichtabsorbierende Verbindungen in der Informationsschicht von optischen Datenträgern
DE10305924 2003-02-13
PCT/EP2004/000878 WO2004072184A1 (fr) 2003-02-13 2004-01-31 Complexes metalliques servant de composes photoabsorbants dans la couche d'information de supports de donnees optiques

Publications (1)

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EP1599548A1 true EP1599548A1 (fr) 2005-11-30

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US (1) US20060280894A1 (fr)
EP (1) EP1599548A1 (fr)
JP (1) JP2006519889A (fr)
CN (1) CN1774481A (fr)
DE (1) DE10305924A1 (fr)
TW (1) TW200501141A (fr)
WO (1) WO2004072184A1 (fr)

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CN110627837A (zh) * 2019-09-10 2019-12-31 齐鲁工业大学 一种检测一氧化碳的金属有机框架材料及制备方法和应用

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DE3162755D1 (en) * 1980-04-30 1984-04-26 Ciba Geigy Ag Azo dyestuffs, methods for their preparation and their use as colouring agents in the silver dyestuff bleaching process
US4661437A (en) * 1984-07-27 1987-04-28 Ciba-Geigy Ag Photographic material with heterocylic azo dye for the silver dye bleach process
JPH11130970A (ja) * 1997-10-31 1999-05-18 Mitsubishi Chemical Corp 含金属アゾ化合物および該化合物を使用した光学記録媒体
JP2002074740A (ja) * 2000-08-25 2002-03-15 Hayashibara Biochem Lab Inc 光記録媒体

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US20060280894A1 (en) 2006-12-14
JP2006519889A (ja) 2006-08-31
CN1774481A (zh) 2006-05-17
DE10305924A1 (de) 2004-08-26
TW200501141A (en) 2005-01-01
WO2004072184A1 (fr) 2004-08-26

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