WO2007042409A1 - Colorants au complexe métallique azoïque à base d'acide barbiturique et leur utilisation dans des couches optiques pour l'enregistrement de données optiques - Google Patents

Colorants au complexe métallique azoïque à base d'acide barbiturique et leur utilisation dans des couches optiques pour l'enregistrement de données optiques Download PDF

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Publication number
WO2007042409A1
WO2007042409A1 PCT/EP2006/066876 EP2006066876W WO2007042409A1 WO 2007042409 A1 WO2007042409 A1 WO 2007042409A1 EP 2006066876 W EP2006066876 W EP 2006066876W WO 2007042409 A1 WO2007042409 A1 WO 2007042409A1
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WIPO (PCT)
Prior art keywords
alkyl
aryl
group
independently
halogenated
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PCT/EP2006/066876
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English (en)
Inventor
Jean-Christophe Graciet
Pascal Steffanut
Lars LÜCKE
Martin Alexander Winter
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Clariant International Ltd
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Publication of WO2007042409A1 publication Critical patent/WO2007042409A1/fr

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    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/2467—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes azo-dyes
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
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    • G11B7/249—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds
    • G11B7/2492—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing organometallic compounds neutral compounds
    • G—PHYSICS
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
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Definitions

  • the present invention relates to barbituric acid based azo metal complex dyes and their use in optical layers for optical data recording, preferably for optical data recording using a laser with a wavelength up to 450 nm.
  • the invention further relates to a write once read many (WORM) type optical data recording medium capable of recording and reproducing information with radiation of blue laser, which employs a barbituric acid based azo metal complex dye in the optical layer.
  • WORM write once read many
  • WORM type optical data recording media like commercial recordable compact discs (CD-R) and recordable digital versatile discs (DVD-R) can contain in the recording layer dyes based on phthalocyanine, hemicyanine, cyanine and metallized azo structures. These dyes are suitable in their respective fields with the laser wavelength criteria.
  • Other general requirements for dye media are strong absorption, high reflectance, high recording sensitivity, enhancement of photosensitivity, low thermal conductivity as well as light and thermal stabilities, durability for storage or non-toxicity.
  • Important criteria are also good read-out stability, which means high number of cycles at a given intensity of laser- light, and sufficient solubilities of the dyes in the organic solvents generally applied in the spin coating process.
  • the optical properties have been changed not only by a change in the optical characteristics and a decrease in the layer thickness resulting from the thermal decomposition of the dye, but also by a deformation of the substrate.
  • CD-R are writable at a wavelength of from 770 to 830 nm and DVD-R, by using more recent compact high-performance red diode lasers, at a wavelength from 600 to 700 nm achieving then a 6- to 8 fold improvement in data packing density in comparison with conventional CDs.
  • Blu-ray ® discs (Blu-ray ® disc is a standard developed by Hitachi Ltd., LG Electronics Inc., Matsushita Electric Industrial Co. Ltd., Pioneer Corporation, Royal Philips Electronics, Samsung Electronics Co. Ltd., Sharp Corporation, Sony Corporation, Thomson Multimedia) or HD-DVD discs (a standard developed by Toshiba and NEC) are going to be the next milestone in optical data recording technology. By these new specifications the data storage may be increased up to 27 Gigabytes per recording layer for a 12 cm diameter disc. By adopting a blue diode laser with a wavelength of 405 nm (GaN or SHG laser diodes), the pit size and track interval can be further reduced, again increasing the storage capacity by an order of magnitude.
  • GaN or SHG laser diodes blue diode laser with a wavelength of 405 nm
  • the optical recording medium comprises preferably a substrate with a guide groove for laser beam tracking, a recording layer, also called optical layer, containing an organic dye as the main component, a reflective layer and a protective layer.
  • a transparent substrate is employed.
  • a transparent substrate one made of a resin such as polycarbonate, polymethacrylate or amorphous polyolefin, one made of glass or one having a resin layer made of radiation curable resin, i.e. photopolymerizable resin, formed on glass, may, for example, be employed.
  • Advanced optical data recording media may comprise further layers, such as protective layers, adhesive layers or even additional optical recording layers.
  • any "halogen” represents F, Cl, Br or I, preferably F, Cl or Br, more preferably F or Cl, even more preferably Cl, if not otherwise stated;
  • any "alkyl” represents linear and branched alkyl, if not otherwise stated;
  • any "alkoxy” represents linear and branched alkoxy, if not otherwise stated;
  • any "alkyl” and any “cycloalkyl” groups being either unsubstituted or substituted by one or more halogen atoms, preferably any halogenated alkyl is selected from the group consisting Of CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 and chloromethyl, if not otherwise stated.
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, Ci-I 0 alkyl, halogenated C 1-10 alkyl, C 5-10 cycloalkyl, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, Ci -I0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, 0-C 6- io-aryl, S-Ce-io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 , NH-SO 2 -R 21 and Ci -I0 alkyl-
  • R 3 and R 8 are independently from each other selected from the group consisting of hydrogen, halogen, CN, NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, C 5-I o cycloalkyl (preferably halogenated alkyl are selected from the group consisting of CF 3 , CF 2 CF 3 and CF 2 CF 2 CF 3 ), C 1-10 alkoxy, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , C 1-10 alkyl, halogenated C 1-10 alkyl, Cs-io-cycloalkyl, C 1-10 alkoxy, NR 21 R 22 , S-C 1-10 alkyl, O-C 6-10 -aryl, S-Ce-io-aryl, SO 2 -NR 21 R
  • NR 21 R 22 S-Ci -I0 alkyl, 0-C 6- io-aryl, S-C 6- io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 and NH-SO 2 -R 21 ;
  • R 4 and R 9 are independently from each other selected from the group consisting of Ci-io alkyl, halogenated Ci -I0 alkyl, Cs -I0 cycloalkyl, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, Ci -I0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, 0-C 6- io-aryl,
  • R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently from each other selected from the group consisting of hydrogen, OH, halogen, CN, NO 2 , Ci-io alkyl, halogenated Ci_io alkyl, Cs-io-cycloalkyl (preferably halogenated alkyl are selected from the group consisting Of CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 and chloromethyl), Ci_io alkoxy, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci-I 0 alkyl, halogenated Ci-I 0 alkyl,
  • NR 21 R 22 S-Ci-I 0 alkyl, 0-C 6- io-aryl, S-C 6- io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 , NH-SO 2 -R 21 and Ci-I 0 alkyl- NR 21 R 22 ;
  • R 21 and R 22 are independently from each other selected from the group consisting of hydrogen, Ci_io alkyl and C 6- Io aryl;
  • R 23 is OH or Ci-I 0 alkoxy.
  • the subject of the invention is a compound of formula (I), wherein M is selected from the group consisting of Ni, Cu, Co, Zn, Fe, Pd, Pt, Mn; X represents O or S;
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 Hs, C 3 H 7 , C 4 Hg 1 unsubstituted phenyl and substituted phenyl with 1 to 3 substituents being independently selected from halogen or C 1-10 alkyl;
  • R 3 and R 8 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , C 3 H 7 (preferably CH(CH 3 ) 2 ), C 4 H 9 (preferably n- butyl), phenyl, CN, halogenated Ci -5 alkyl (preferably halogenated
  • Ci- 5 alkyl is selected from the group consisting of CF 3 , CF 2 CF 3 and
  • R 4 and R 9 are independently from each other selected from the group consisting of
  • R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently from each other selected from the group consisting of hydrogen, Cl, CN, Br,
  • Ci -4 alkyl preferably halogenated Ci -4 alkyl is selected from the group consisting of CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 and chloromethyl
  • Ci -4 -alkoxy preferably NO 2 and SO 2 -NR 21 R 22 ; with R 21 and R 22 being independently selected from the group consisting of hydrogen and Ci -4 alkyl; and with halogen being preferably F, Cl or Br, more preferably F or Cl.
  • subject of the present invention is a compound of formula (I), wherein
  • M is selected from the group consisting of Ni, Cu, Co, Zn and Mn;
  • X represents O or S;
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , unsubstituted phenyl and substituted phenyl with 1 or 2 substituents being independently selected from Cl or Ci-4-alkyl;
  • R 3 and R 8 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , C 3 H 7 (preferably CH(CH 3 ) 2 ), C 4 H 9 (preferably n- butyl), halogenated Ci -3 alkyl (preferably halogenated Ci -3 alkyl is selected from the group consisting of CF 3 , CF 2 CF 3 and CF 2 CF 2 CF 3 ); R 4 and R 9 are independently from each other CH 3 or C 2 H 5 ; R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently from each other selected from the group consisting of hydrogen, Cl, CN, Br, , NO 2 , C i-4 alkyl (preferably CH 3 or C2H5) and halogenated Ci -4 alkyl (preferably halogenated Ci -4 alkyl is selected from the group consisting OfCF 3 , CF
  • R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently from each other selected from the group consisting of hydrogen, Cl, Ci -4 alkyl and halogenated Ci -4 alkyl (preferably halogenated Ci -4 alkyl is selected from the group consisting of CF 3 , CF 2 CF 3 and CF 2 CF 2 CF 3 ); more particular preferred R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 16 , R 17 and R 18 are hydrogen and R 5 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl, CF 3 and CF 2 CF 3 ; and in another more particularly preferred aspect of the invention, R 6 , R 7 , R 10 , R 16 , R 17 and R 18 are hydrogen, R 5 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl,
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , phenyl and substituted phenyl with one or two substituents being independently selected from the group consisting of Cl, CH 3 and C 2 H 5 ; more particularly preferred R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , phenyl, chlorophenyl and dichlorophenyl.
  • X represents S.
  • the subject of the invention is a compound of formula (II),
  • M is selected from Ni, Zn, Cu, Co and Mn;
  • X represents O or S
  • R 3 and R 8 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 and CF 3 ;
  • R 5 , R 11 , R 12 , R 13 ,R 14 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl, CH 3 , C 2 H 5 , CF 3 and CF 2 CF 3 ;
  • the subject of the invention is a compound of formula (II), wherein
  • M is selected from Ni, Zn, Cu and Co, especially from Cu and Co; more especially M represents Cu;
  • X represents S
  • R 3 and R 8 are independently from each other selected from the group consisting of
  • R 5 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl, CF 3 and CF 2 CF 3 ;
  • R 11 , R 12 , R 13 and R 14 are independently from each other selected from the group consisting of hydrogen and Cl;
  • the subject of the invention is a compound of formula (II), wherein M is selected from Cu and Co, and preferably represents Cu; X represents S; R 3 and R 8 are independently from each other selected from the group consisting of
  • R 5 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl, CF 3 and CF 2 CF 3 ;
  • R 11 , R 12 , R 13 and R 14 are same and represent either hydrogen or Cl.
  • the compounds of formula (I) are prepared by complexing reaction of one equivalent of an azo ligand of the formula (III) and one equivalent of a azo ligand of the formula (IV) with a one equivalent of a metal salt,
  • M represents a metal atom
  • X represents O or S
  • R 1 and R 2 are independently from each other selected from the group consisting of hydrogen, C 1-10 alkyl, halogenated C 1-10 alkyl, C 5-10 cycloalkyl, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, Ci -I0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, 0-C 6- io-aryl, S-Ce-io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 , NH-SO 2 -R 21 and Ci -I0 alkyl-NR 21
  • R and R are independently from each other selected from the group consisting of hydrogen, halogen, CN, NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs -I0 cycloalkyl (preferably halogenated alkyl are selected from the group consisting of CF 3 , CF 2 CF 3 and CF 2 CF 2 CF 3 ), Ci -I0 alkoxy, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, Ci -I0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, 0-C 6- io-aryl,
  • R 4 and R 9 are independently from each other selected from the group consisting of Ci-io alkyl, halogenated C 1-10 alkyl, C 5-I o cycloalkyl, unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , C 1-10 alkyl, halogenated C 1-10 alkyl, C 5- io-cycloalkyl, C 1-10 alkoxy, NR 21 R 22 , S-C 1-10 alkyl, O-C 6-10 -aryl, S-Ce-io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO- R 21
  • R 5 , R 6 , R 7 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently from each other selected from the group consisting of hydrogen, OH, halogen, CN, NO 2 , Ci-io alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl (preferably halogenated alkyl are selected from the group consisting of CF 3 , CF 2 CF 3 ,
  • Ci -I0 alkoxy unsubstituted phenyl, substituted phenyl with 1 to 4, preferably 1 to 3, more preferably 1 or 2 substituents being independently selected from the group consisting of OH, halogen, CN, CF 3 , NO 2 , Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, Ci -I0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, O-C 6- i 0 -aryl,
  • Ci -I0 alkyl Ci -I0 alkyl, halogenated Ci -I0 alkyl, Cs-io-cycloalkyl, C 1- I 0 alkoxy, NR 21 R 22 , S-Ci -I0 alkyl, O-C 6- i 0 -aryl, S-C 6- i 0 -aryl, SO 2 - NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 , NH-SO 2 -R 21 and Ci-I 0 alkyl-NR 21 R 22 ,
  • NR 21 R 22 S-Ci-io alkyl, 0-C 6- io-aryl, S-C 6- io-aryl, SO 2 -NR 21 R 22 , CO-R 23 , SO 2 R 23 , CO-NR 21 R 22 , NH-CO-R 21 , NH-SO 2 -R 21 and Ci-I 0 alkyl- NR 21 R 22 :
  • R >21 and R ,22 are independently from each other selected from the group consisting of hydrogen, C 1-10 alkyl and C 6-10 aryl;
  • R 23 is OH or Ci-io alkoxy.
  • the compounds of formula (II) are prepared by complexing reaction of one equivalent of an azo ligand of the formula (HIb) and one equivalent of a azo ligand of the formula (IVb) with a one equivalent of a metal salt,
  • M is selected from Ni, Zn, Cu, Co and Mn;
  • X represents O or S;
  • R 3 and R 8 are independently from each other selected from the group consisting of hydrogen, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 and CF 3 ;
  • R 5 , R 11 , R 12 , R 13 , R 14 and R 15 are independently from each other selected from the group consisting of hydrogen, Cl, CH 3 , C 2 H 5 , CF 3 , and CF 2 CF 3 .
  • the metal salt is a divalent metal salt with the metal preferably selected from the group consisting of Ni, Cu, Co, Zn, Al, Fe, Pd, Pt, Cr, Mn. Divalent salts of these metals are preferably sulfates, chlorides and acetates and their respective hydrates.
  • Preferred metal salts are derived from Ni, Cu, Co, Zn, Cr and Mn. More preferred metal salts are for example nickel-, copper-, cobalt-, zinc-, chromium- or manganese sulfate; nickel-, copper-, cobalt-, zinc-, chromium- or manganese chloride or nickel-, copper-, cobalt-, zinc-, chromium- or manganese acetate and their respective hydrates, especially Cu(SO 4 ) 2 , Cu(SO 4 ) 2 *5 H 2 O, CuCl 2 , Ni(OAc) 2 *4 H 2 O, MC1 2 *6 H 2 O, Co(SO 4 ) 2 , Zn(OAc) 2 *4 H 2 O.
  • metal salts are Ni(OAc) 2 *4 H 2 O, Cu(SO 4 ) 2 , Cu(SO 4 ) 2 *5 H 2 O, Co(SO 4 ) 2 , Zn(OAc) 2 *4 H 2 O, especially Cu(SO 4 ) 2 and Cu(SO 4 ) 2 *5 H 2 O.
  • the azo ligands of formula (III), (HIb), (IV) and (IVb) are prepared by azo coupling reaction of the respective diazo component and the respective coupling agent.
  • the diazo component is prepared by diazotization reaction of the respective amine compound.
  • the azo coupling reaction may be carried out in water, non-aqueous solvents and in mixtures thereof.
  • Suitable non-aqueous solvents are alcohols such as methanol, ethanol, propanol, butanol, pentanol, etc., dipolar aprotic solvents such as acetone, DMF, DMSO, NMP and water-immiscible solvents such as toluene or chlorobenzene.
  • the azo coupling reaction is carried out in water.
  • the coupling is preferably carried out in a stoichiometric ratio of coupling component and diazo component.
  • the coupling is generally done at temperatures between -30 0 C to 100 0 C, preference being given to temperatures of -10 0 C to 30 0 C, and particular preference to temperatures of -5°C to 20 0 C.
  • the coupling may be carried out in an acidic as well as an alkaline medium. Preference is given to pH ⁇ 10, particular preference to pH from between 3 to 9.0.
  • the compounds of formula (I) and (II) are prepared by complexing reaction of a solution of one equivalent of a metal salt with a boiling solution of one equivalent of the azo ligand of formula (III) and (HIb) respectively and one equivalent of the azo ligand of formula (IV) and (IVb) respectively.
  • a solution of one equivalent of a metal salt with a boiling solution of one equivalent of the azo ligand of formula (III) and (HIb) respectively and one equivalent of the azo ligand of formula (IV) and (IVb) respectively.
  • the combined amounts of the azo ligands should preferably be equal to two equivalents of the metal salt.
  • more than one metal salt preferably a mixture of 2 or 3 metal salts, in the required stoichiometric amounts with regard to the azo ligands; and a combination of these measures is also possible.
  • the precipitate is isolated following standard methods, preferably by filtration.
  • the solvents that can be used in the complexing reaction are water, solvents and mixtures thereof.
  • the solvents are preferably selected from the group consisting of Ci-S alcohols, nitriles, preferably acetonitrile, acetone, aromatic solvents such as toluene or chlorobenzene, DMF, DMSO, NMP.
  • More preferred solvents used for the complexing reaction are Ci-S alcohols, especially ethanol, and acetonitrile.
  • metal salt already at an earlier stage of the synthesis of the compounds of formula (I) or their precursors, preferably before, during or after the azo coupling reaction, more preferably after the azo coupling reaction to the resulting suspension or solution of the azo ligands.
  • the azo ligands are isolated and dried after synthesis, and the complexing reaction is carried out in a separate step.
  • a further subject of the invention is therefore a process for the preparation of the compounds of formula (I), as well as of the compounds of formula (I) in all the preferred aspects of the formula (I) as described above, by a complexing reaction of the azo ligands of formula (III) and (IV), with a metal salt; and further a process for the preparation of the compounds of formula (II), as well as of the compounds of formula (II) in all the preferred aspects of the formula (II) as described above, by a complexing reaction of the azo ligands of formula (HIb) and (IVb), with a metal salt; with the azo ligands preferably prepared by a azo coupling reaction of the respective diazo components and the respective coupling agents.
  • a further subject of the invention is the use of the compounds of formula (I) or (II) and the use of the compounds of formula (I) or (II) in all the preferred aspects of the formula (I) or (II) as described above, in an optical layer, preferably for optical data recording.
  • a further subject of the invention is the use of the compounds of formula (I) or (II) and the use of the compounds of formula (I) or (II) in all the preferred aspects of the formula (I) or (II) as described above, as a dye in an optical layer, preferably for optical data recording.
  • a further subject of the present invention is an optical layer comprising at least one compound of formula (I) or (II) and the use of said optical layer for optical data recording media.
  • An optical layer according to the invention may also comprise a mixture of two or more, preferably of two or three, more preferably of two compounds of formula (I) or (II).
  • a further subject of the invention therefore is an optical data recording medium comprising an optical layer comprising at least one compound of formula (I) or (II).
  • the compounds of formula (I) or (II) provide for particularly preferable properties when used in optical layers for optical data recording media according to the invention.
  • the invention relates to a method for producing optical layers on a substrate comprising the following steps
  • the substrate which functions as support for the layers applied thereto, is advantageously semi-transparent (transmittance T>10%) or preferably transparent (transmittance T>90%).
  • the support can have a thickness of from 0.01 to 10 mm, preferably from 0.1 to 5 mm.
  • Suitable substrates are, for example, glass, minerals, ceramics and thermosetting or thermoplastic plastics.
  • Preferred supports are glass and homo- or co-polymeric plastics.
  • Suitable plastics are, for example, thermoplastic polycarbonates, polyamides, polyesters, polyacrylates and polymethacrylates, polyurethanes, polyolefins, polyvinyl chloride, polyvinylidene fluoride, polyimides, thermosetting polyesters and epoxy resins.
  • the most preferred substrates are polycarbonate (PC) or polymethylmethacrylate (PMMA).
  • the substrate can be in pure form or may also comprise customary additives, for example UV absorbers as light-stabilizers for the optical layer.
  • the substrate is advantageously transparent over at least a portion of the range from 350 to 500 nm, so that it is permeable to at least 90% of the incident light of the writing or readout wavelength.
  • Organic solvents are selected from Ci-S alcohol, halogen substituted Ci-S alcohols, Ci-S ketone, Ci-S ether, halogen substituted Ci -4 alkane, nitriles, preferably acetonitrile, or amides, or mixtures thereof.
  • Ci-S alcohols or halogen substituted Ci-S alcohols are for example methanol, ethanol, isopropanol, diacetone alcohol (DAA), 2,2,3, 3-tetrafiuoro-l-propanol (TFP), trichloroethanol, 2-chloroethanol, octafiuoropentanol or hexafluorobutanol, more preferred 2,2,3,3-tetrafiuoro-l-propanol.
  • Ci-S ketones are for example acetone, methylisobutylketone, methylethylketone, or 3-hydroxy-3-methyl-2-butanone.
  • Ci -4 alkanes are for example chloroform, dichloromethane or 1-chlorobutane.
  • Preferred amides are for example dimethylformamide or dimethylacetamide.
  • Coating methods are, for example, immersion, pouring, brush-coating, blade- application and spin-coating, as well as vapor-deposition methods carried out under a high vacuum.
  • pouring methods solutions in organic solvents are generally used.
  • solvents are employed, care should be taken that the supports used are insensitive to those solvents.
  • the optical layer is preferably applied by spin- coating with a dye solution.
  • Optical layer also called dye layer or recording layer
  • the optical layer is preferably arranged between the transparent substrate and the reflecting layer.
  • the thickness of the recording layer is from 10 to 1000 nm, preferably from 30 to 300 nm, more preferably from 70 to 250 nm, especially about 80 nm, for example from 60 to 120 nm.
  • the optical layer comprises a compound of formula (I) or (II) preferably in an amount sufficient to have a substantial influence on the refractive index, for example at least 30% by weight of the total weight of the optical layer, more preferably at least 60% by weight, most preferably at least 80% by weight.
  • stabilizers for example 1 O 2 -, triplet- or luminescence quenchers, melting-point reducers, decomposition accelerators or any other additives that have already been described in optical data recording media.
  • stabilizers or fluorescence-quenchers are added if desired.
  • Stabilizers, 1 O 2 -, triplet- or luminescence-quenchers are, for example, metal complexes of N- or S-containing enolates, phenolates, bisphenolates, thiolates or bisthiolates, hindered phenols and derivatives thereof such as o-hydroxyphenyl-triazoles or -triazines or other UV absorbers, such as hindered amines (TEMPO or HALS, as well as nitroxides or NOR-HALS), and also as cations diimmonium, ParaquatTM or Orthoquat salts, such as ® Kayasorb IRG 022, ® Kayasorb IRG 040, optionally also as radical ions, such as N,N,N',N'-tetrakis(4-dibutylaminophenyl)-p-phenylene amine-ammonium hexafluorophosphate, hexafluoroantimonate or perchlorate.
  • the latter are available from
  • the present invention provides for an optical layer suitable for high-density recording material, e.g. of the WORM disc format, in a laser wavelength range of from 350-450nm, preferably around 405 nm.
  • a method for producing an optical data recording medium comprising an optical layer according to the invention usually comprises the following additional steps
  • the application of the metallic reflective layer is preferably effected by sputtering, vapor-deposition in vacuum or by chemical vapor deposition (CVD).
  • the sputtering technique is especially preferred for the application of the metallic reflective layer.
  • Reflecting materials suitable for the reflective layer include especially metals, which provide good reflection of the laser radiation, used for recording and playback, for example the metals of Main Groups III, IV and V and of the Sub-groups of the Periodic Table of the Elements.
  • Special preference is given to a reflective layer of aluminum, silver, copper, gold or an alloy thereof, on account of their high reflectivity and ease of production.
  • Cover layer also called protective layer
  • cover layer Materials suitable for the cover layer include plastics, which are applied in a thin layer to the support or the uppermost layer either directly or with the aid of adhesive layers.
  • the material of the cover layer may for example be the same as the material of the substrate. It is advantageous to select mechanically and thermally stable plastics having good surface properties, which may be modified further.
  • the plastics may be thermosetting plastics and thermoplastic plastics. Preference is given to radiation-cured (e.g. using UV radiation) protective layers, which are particularly simple and economical to produce.
  • radiation-curable materials are known. Examples of radiation-curable monomers and oligomers are acrylates and methacrylates of diols, trio Is and tetrols, polyimides of aromatic tetracarboxylic acids and aromatic diamines having Ci-C4alkyl groups in at least two ortho-positions of the amino groups, and oligomers with dialkylmaleinimidyl groups, e.g. dimethyl maleinimidyl groups.
  • a high-density optical data recording medium therefore preferably is a recordable optical disc comprising: a first substrate, which is a transparent substrate with grooves, a optical layer (recording layer), which is formed on the first substrate surface using the compounds of formula (I) or (II), a reflective layer formed on the optical layer, a second substrate, which is a transparent substrate connected to the reflective layer with an attachment layer.
  • the optical data recording medium according to the invention is preferably a recordable optical disc of the WORM type. It may be used, for example, as a playable HD-DVD (high density digital versatile disc) or Blu-ray ® disc, as storage medium for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.
  • WORM high density digital versatile disc
  • Blu-ray ® disc as storage medium for a computer or as an identification and security card or for the production of diffractive optical elements, for example holograms.
  • optical data recording media according to the invention may also have additional layers, for example interference layers. It is also possible to construct optical data recording media having a plurality of (for example two) recording layers. The structure and the use of such materials are known to the person skilled in the art. Preferred, if present, are interference layers that are arranged between the recording layer and the reflecting layer and/or between the recording layer and the substrate and consist of a dielectric material Of TiO 2 , Si 3 N 4 , ZnS or silicone resins.
  • optical data recording media according to the invention can be produced by processes known in the art.
  • the structure of the optical data recording medium according to the invention is governed primarily by the readout method; known function principles include the measurement of the change in the transmission or, preferably, in the reflection, but it is also known to measure, for example, the fluorescence instead of the transmission or reflection.
  • the optical data recording medium is structured for a change in reflection
  • the following structures can be used: transparent support / recording layer (optionally multilayered) / reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent) / reflective layer / recording layer and, if expedient, transparent protective layer.
  • transparent support / recording layer optionally multilayered
  • reflective layer and, if expedient, protective layer (not necessarily transparent); or support (not necessarily transparent) / reflective layer / recording layer and, if expedient, transparent protective layer.
  • the light detector is located on the same side as the light source.
  • the first-mentioned structure of the recording material to be used according to the invention is generally preferred.
  • the optical data recording medium is structured for a change in light transmission, the following different structure comes into consideration: transparent support/ recording layer (optionally multilayered) and, if expedient, transparent protective layer.
  • the light for recording and for readout can be incident either from the support side or from the recording layer side or, where applicable, from the protective layer side, the light detector in this case always being located on the opposite side.
  • Suitable lasers are those having a wavelength of 350-500 nm, for example commercially available lasers having a wavelength of 405 to 414 nm, especially semi-conductor lasers.
  • the recording is done, for example, point for point, by modulating the laser in accordance with the mark lengths and focusing its radiation onto the recording layer. It is known from the specialist literature that other methods are currently being developed which may also be suitable for use.
  • the process according to the invention allows the storage of information with great reliability and stability, distinguished by very good mechanical and thermal stability and by high light stability and by sharp boundary zones of the pits. Special advantages include the high contrast, the low jitter and the surprisingly high signal/noise ratio, so that excellent readout is achieved.
  • the readout of information is carried out according to methods known in the art by registering the change in absorption or reflection using laser radiation.
  • the invention accordingly relates also to a method for the optical data recording, storage and playback of information, wherein an optical data recording medium according to the invention is used.
  • the recording and the playback advantageously take place in a wavelength range of from 350 to 500 nm.
  • the compounds of formula (I) or (II) provide for particularly preferable properties when used in optical layers for optical data recording media according to the invention. They possess the required optical characteristics, demonstrated when used in the form of a solid film: • an advantageously homogeneous, amorphous and low-scattering optical layer,
  • a decomposition point DP in the preferred temperature range between 220 0 C and 350 0 C, more precisely 230 0 C to 300 0 C
  • Recording performance of a compound is related to specific parameters measured on disc like:
  • the absorption edge is surprisingly steep even in the solid phase.
  • the compounds of formula (I) or (II) also show a narrow decomposition temperature of 250-350 0 C, fitting with the thermal requirements. Additionally, these compounds show a high solubility in organic solvents, which is ideal for the spin-coating process to manufacture optical layers.
  • ⁇ max and ⁇ values of a compound are determined by using an UV- vis spectrophotometer, the compound was dissolved in CH 2 Cl 2 , DMSO or TFP. The values are obtained by balancing the measurements performed on compound solutions at three different concentrations.
  • Thermal Decomposition Decomposition point (DP) and heat release (HR)
  • DP Decomposition point
  • HR heat release
  • DP and HR the compound is incorporated into a sealed aluminum pan. Analysis conditions are as following: Temperature range from 25 to 400 0 C, heating rate 10°C/min, nitrogen flow of 50 ml/min. Values are determined by single measurement.
  • PRSNR PRSNR
  • Annex H of Version 0.9 PART 1 Physical Specifications
  • DVD Specifications for High Density Read-Only Disk
  • PRSNR and SbER are measured in a state in which information has been recorded in the adjacent tracks.
  • Ligand (1) A mixture of 20.7 g of 4-aminoantipyrine, 130 ml of water and 32 g of concentrated hydrochloric acid (30% w/w) was gradually admixed with 24.9 ml of sodium nitrite (33% w/v) at 0 0 C. After 1 hour of reaction at 0 0 C, the orange diazotization solution was added drop wise to an alkaline solution of 20.4 g of l,3-diethyl-2-thiobarbituric acid while maintaining pH at 7.5-9 with sodium hydroxide (30% w/w). The batch was stirred 3 hours, then filtered with suction. The precipitate was washed with water and dried. 38.2 g of azo ligand of formula (1) was obtained.
  • azo ligand (10) A mixture of 10.4 g of 4-aminoantipyrine, 50 ml of water and 16.1 g of concentrated hydrochloric acid (34% w/v) was gradually admixed with 12.4 ml of sodium nitrite (33% w/v) at 0 0 C; After 1 hour of reaction at 0 0 C, the orange diazotization solution was added dropwise to an alkaline solution of 7.5 g of 1,3- indanedione, 200ml of water and 15.9g of sodium carbonate to attain pH at 7.5-8. The batch was stirred 30 minutes, and 17ml of acetic acid is added to adjust to pH 5. Then the batch is filtered with suction. The precipitate was washed with water and dried. The presscake yielded 17.8 g of azo ligand of the following formula (10).
  • Azo ligand 11 was prepared according to example 10 using tetrachloroindandione in place of 1,3-indanedione.
  • azo ligand of formula (1) prepared according to example 1 and 3.3 g of azo ligand of formula (10) prepared according to example 10 are suspended in 100 ml of ethanol together with 1.5 g of sodium acetate. After heating up to reflux, 2.3 g of copper sulfate penta hydrate in 35 ml of water are added for over one hour, whereupon a dark orange suspension of the copper complex dye results. The suspension is cooled down to room temperature and the resulting precipitate is stirred for one hour, filtered and the residue washed salt free with deionized water and dried. 15.8 g of the copper complex dye compound of the formula (12) is obtained.
  • the complexing reaction was repeated with one ligand of each example 2 to 9 prepared according to examples 2 to 9 and one ligand of example 10 prepared according to example 10, and also with one ligand of example 2 prepared according to examples 2 and one ligand of example 11 prepared according to example 11 ; and with the respective metal salt according to Table (A), to yield metal complex dye compounds of formulae (12) to (21) of the examples (12) to (21). Details are given in Table (A).
  • the optical and thermal properties of the compounds of formula (I) were studied.
  • the compounds of formula (I) show high absorption at the desired wavelengths.
  • the shapes of the absorption spectra that still remain critical to the disc reflectivity and formation of clean mark edges, are composed of one major band, comprised in a range offrom 350 to 500 nm. More precisely, n values of the refractive index were evaluated between 1.0 and 2.7. Light stabilities were found comparable to commercial dyes which are already stabilized with quenchers for the use in optical data recording.
  • Sharp threshold of thermal decomposition within the required temperature range characterizes the compounds of formula (I) which are desirable for the application in optical layers for optical data recording.
  • a 100 ⁇ m thick silver layer is then applied to the recording layer by atomization.
  • a 6 ⁇ m thick protective layer of a UV curable photopolymer (650-020, DSM) is applied thereto by means of spincoating.
  • a second substrate is provided to combine with the resin protection layer using an attachment layer. This completes the manufacturing of a high- density recordable optical disc, the optical data recording medium.
  • Evaluation tests are performed using an optical disk evaluation device available from Pulse Tech Co., Ltd.
  • the testing conditions are the following ones:
  • Constant linear velocity (CLV) 6.61 m/sec. • Track pitch: 400 nm
  • a test for evaluating a degree of degradation due to repetition reproduction is conducted for each of the write-once optical disks made for the described dye recording layers. Readings are carried out at a reading laser power of 0.4 mW and the degrees of degradation of PRSNR and SbER are then measured. Maximum cycle number was found within the specifications.

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Abstract

La présente invention concerne des colorants au complexe métallique azoïque à base d'acide barbiturique et leur utilisation dans des couches optiques pour l'enregistrement de données optiques, de préférence pour l'enregistrement de données optiques utilisant un laser avec une longueur d'onde jusqu'à 450 nm. L'invention concerne en outre un support d'enregistrement de type non réinscriptible (WORM) en mesure d'enregistrer et de reproduire des informations par le rayonnement de laser bleu, qui emploie un colorant au complexe métallique azoïque à base d'acide barbiturique dans la couche optique.
PCT/EP2006/066876 2005-10-12 2006-09-29 Colorants au complexe métallique azoïque à base d'acide barbiturique et leur utilisation dans des couches optiques pour l'enregistrement de données optiques WO2007042409A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008138812A2 (fr) * 2007-05-09 2008-11-20 Clariant Finance (Bvi) Limited Colorants azoïques à base de pyridinone et leurs sels complexes métalliques
US11034669B2 (en) 2018-11-30 2021-06-15 Nuvation Bio Inc. Pyrrole and pyrazole compounds and methods of use thereof

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DE450819C (de) * 1924-12-24 1927-10-20 Chemische Ind Ges Verfahren zur Herstellung von chromhaltigen Azofarbstoffen
DE1076078B (de) * 1958-02-06 1960-02-25 Ciba Geigy Verfahren zum Faerben und Bedrucken von im wesentlichen aus Polyacrylnitril bestehenden Fasern
US2993884A (en) * 1958-02-06 1961-07-25 Ciba Ltd Metal complexes of monoazo-dyestuffs
EP1191526A2 (fr) * 2000-08-25 2002-03-27 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Supports d'enregistrement optiques
US20020091241A1 (en) * 2000-11-02 2002-07-11 Industrial Technology Research Institute Azo-metal complex dye and method for producing the same and its use for a high density optical disc recording medium
US20040161701A1 (en) * 2000-02-10 2004-08-19 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenyujo Cyanine dyes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE450819C (de) * 1924-12-24 1927-10-20 Chemische Ind Ges Verfahren zur Herstellung von chromhaltigen Azofarbstoffen
DE1076078B (de) * 1958-02-06 1960-02-25 Ciba Geigy Verfahren zum Faerben und Bedrucken von im wesentlichen aus Polyacrylnitril bestehenden Fasern
US2993884A (en) * 1958-02-06 1961-07-25 Ciba Ltd Metal complexes of monoazo-dyestuffs
US20040161701A1 (en) * 2000-02-10 2004-08-19 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenyujo Cyanine dyes
EP1191526A2 (fr) * 2000-08-25 2002-03-27 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Supports d'enregistrement optiques
US20020091241A1 (en) * 2000-11-02 2002-07-11 Industrial Technology Research Institute Azo-metal complex dye and method for producing the same and its use for a high density optical disc recording medium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008138812A2 (fr) * 2007-05-09 2008-11-20 Clariant Finance (Bvi) Limited Colorants azoïques à base de pyridinone et leurs sels complexes métalliques
WO2008138812A3 (fr) * 2007-05-09 2009-11-26 Clariant Finance (Bvi) Limited Colorants azoïques à base de pyridinone et leurs sels complexes métalliques
US11034669B2 (en) 2018-11-30 2021-06-15 Nuvation Bio Inc. Pyrrole and pyrazole compounds and methods of use thereof

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